PHYSICAL REVIEW A 81, 022709 (2010)

Electron-impact study of the PH radical using the R-matrix method

Jasmeet Singh Rajvanshi* and K. L. Baluja†

Department of Physics and Astrophysics, University of Delhi, Delhi 110007, India
(Received 23 October 2009; published 10 February 2010)
The PH radical is an interesting case to study because of its π 2 electronic configuration, which leads to the
three low-lying electronic states, X 3  − , a 1 , and b 1  + . The singlet states possess long lifetimes, because
direct combination with the ground state is not allowed. This is similar to the O2 case. The R-matrix method
is employed to calculate elastic differential and integral cross sections, momentum-transfer cross sections,
and inelastic cross sections. The energy range is 0–10 eV. The Hartree-Fock ground-state configuration of PH is
1σ 2 2σ 2 3σ 2 1π 4 4σ 2 5σ 2 2π 2 . We have included thirty-seven target states in the trial wave function of the scattering
system in our best model. Each target state is represented by a configuration interaction (CI) wave function. In
our CI model, we freeze ten electrons in orbitals 1σ , 2σ , 3σ, and 1π ; the remaining six electrons are free to move
among the seven orbitals 4σ , 5σ , 6σ , 7σ , 8σ , 2π, and 3π . Our CI model yields a dipole moment of 0.67 D at the
equilibrium PH bond length, Re , of 2.687 a0 ; this dipole moment compares favorably with the experimental value
0.70 D. We have carried our scattering calculations in one state with the CI wave function and thirty-seven-state
model. We have detected a stable anionic bound state 2 B1 of PH at various bond lengths of PH molecule. The
vertical electron affinity value is 0.97 eV, which is in excellent agreement with experimental value of 1.00 eV.
We have included up to g partial waves in the scattering calculations. The contribution of higher partial waves is
accounted for by using a Born-closure procedure.

DOI: 10.1103/PhysRevA.81.022709 PACS number(s): [Link], [Link], [Link]

I. INTRODUCTION P(2 D) + H(2 S); and b 1  + correlates to P(2 P ) + H(2 S). The
Electron-molecule collisions initiate almost all the chem- excited states mentioned here correlate to different dissociation
istry relevant to the study of the environment and the limits but have nearly the same equilibrium bond length [4].
plasma processing of materials. There are several reasons Bruna et al. [4] have carried out the study on PH by calculating
for studying the electron impact on polyatomic molecules. potential curves for the low-lying valence states by employing
The electron-molecule cross sections form an important a multireference double-excitation method. Slater orbitals
input used to model complex processes in low-temperature are used to represent P and H atoms. They also reported a
plasmas, which are useful in the fabrication of computer variety of spectroscopic constants. Senekowitsch et al. [5]
chips. There is a vast literature available on the spectroscopic have employed the highly correlated multiconfigurational
study of PH. However, there are no calculations available self-consistent field configuration interaction wave function
on electron impact with the PH molecule. The aim of the (MCSCF-CI) to calculate potential energy, dipole moment,
present work is to remedy this deficiency. The spectrum of and electronic-transition moment functions for the A 3 –
PH may occur in the sun [1] and cool stellar atmospheres X 3  − states of PH. The A 3 –X 3  − electronic transition in
[2]. Cade and Huo [3] have carried out an exhaustive study the PH radical has been extensively studied by absorption [6,7]
of potential energy function and spectroscopic constants for and emission [8] experiments. Experimental determination of
the second-row hydrides using the Hartree-Fock-Roothaan molecular parameters for the A 3  and X 3  − states has been
wave function, which is believed to very closely approximate carried out by Rostas et al. [8] using rotational analysis of
the true Hartree-Fock wave function. The PH radical, like the PH A 3 –X 3  − band spectrum. Meyer and Rosmus [9]
its isovalent first-row radical NH, is an open-shell system have calculated potential energy curves and dipole moment
with unpaired π 2 ground-state electronic configuration. This functions for the ground states of the first-row and second-row
configuration gives rise to three low-lying electronic states, diatomic hydrides by using partially nonorthogonal pseudonat-
X 3  − , a 1 , and b 1  + . Just like the case of O2 , the singlet ural orbitals in configuration interaction (CI) formalism and
states cannot decay to the triplet ground state because these coupled electron pair approximation (CEPA). Dipole moments
transitions are forbidden because of spin change and hence of first five low-lying states of PH and transition moments
possess long lifetimes. The next set of excited states A 3  and of the A 3 –X 3  − transition have been computed by an
c 1  arises from the electronic configuration σ π 3 . The first al- effective ab initio effective valence shell Hamiltonian method
lowed transition, A 3 –X 3  − , has been studied spectroscop- [10]. The first experimental study of photoionization of PH
ically [4]. The ground state X 3  − correlates to the separated was carried out by Berkowitz and Cho [11] from threshold
atom limit P(4 S) + H(2 S); a 1 , A 3 , and c 1  correlate to to 1040 Å. Gan et al. [12] made an ab initio calculation
of several excited states of PHn (n = 1–3) by a variety of
CI calculations at various levels of sophistication. Molecular
constants of low-lying electronic states of PX (X = H, F, and
*
Also at Keshav Mahavidyalaya, Physics and Electronics Depart- Cl) have been determined [13] by Møller-Plesset perturbation
ment, University of Delhi; rajvanshi jasmeet@[Link] theory. The heat of formation of PH at 298 K has been
†
kl baluja@[Link] determined to be 56.78 kcal/mol by Ricca et al. [14], who used

1050-2947/2010/81(2)/022709(8) 022709-1 ©2010 The American Physical Society

JASMEET SINGH RAJVANSHI AND K. L. BALUJA PHYSICAL REVIEW A 81, 022709 (2010)

the Becke three-parameter Lee-Yang-Parr hybrid functional (N + 1) electrons in the truncated space, where there are
(B3LYP) approach with the 6-31 G∗ basis set. Reddy et al. [15] N target electrons and a single scattering electron. Most of
determined the dissociation energy for the ground electronic the physics of the scattering problem is contained in this
state of PH to be 3.10 eV, which is in good accord with the (N + 1) electron bound-state molecular-structure calculation.
experimental value [16,17]. Outside the sphere, only long-range multipolar interactions
The present study uses the ab initio R-matrix method for between the scattering electron and the various target states
the low-energy scattering of the PH molecule in the fixed are included. Because only direct potentials are involved in the
nuclei approximation. The calculations use the UK molecular outer region, a single center approach is used to describe the
R-matrix code [18,19]. The R-matrix method has an advantage scattering electron via a set of coupled differential equations.
over other scattering methods because it provides cross The R matrix is a mathematical entity that connects the two
sections at a large number of scattering energies efficiently. regions. It describes how the scattering electron enters and
It also has the ability to include correlation effects and give leaves the inner region. In the outer region, the R matrix on the
an adequate representation of several excited states of the boundary is propagated outward [25,26] until the inner-region
molecule [20]. We are interested in the low-energy region solutions can be matched with asymptotic solutions, thus
(
10 eV), which is a favorite ground for the R-matrix method. yielding the physical observables such as cross sections. We
The incoming electron can occupy one of the many unoccupied include only the dipole and quadrupole moments in the outer
molecular orbitals or can excite any of the occupied molecular region.
orbitals as it falls into another one. These processes give In the polyatomic implementation of the UK molecular
rise to the phenomenon of resonances forming a negative R-matrix code [18,19], the continuum molecular orbitals
molecular ion for a finite time before the resonance decays are constructed from atomic Gaussian-type orbitals (GTOs)
into energetically open channels. using basis functions centered on the center of gravity of
Electron-scattering calculations are performed at one-state the molecule. The main advantage of GTOs is that integrals
CI and close-coupling approximation in which we have involving them over all space can be evaluated analytically
retained thirty-seven target states in the R-matrix formalism. in closed form. However, a tail contribution is subtracted to
The integrated elastic, differential, and momentum cross yield the required integrals in the truncated space defined by
sections for electron impact on the PH molecule from its the inner region [18].
ground state are reported. The excitation cross sections from The target molecular orbital space is divided into core
the ground state to a few low-lying excited states have also (inactive), valence (active), and virtual orbitals. The target
been calculated. We have also computed the binary-encounter- molecular orbitals are supplemented with a set of continuum
Bethe (BEB) ionization cross section [21,22]. The BEB cross orbitals, centered on the center of gravity of the molecule.
sections depend only on the binding energies, kinetic energies, The continuum basis functions used in polyatomic R-matrix
occupation number of the occupied molecular orbitals of the calculations are Gaussian functions and do not require fixed
target, and energy of the incident electron. boundary conditions. First, target and continuum molecular
orbitals are orthogonalized using Schmidt orthogonalization.
Then symmetric or Löwdin orthogonalization is used to
II. METHOD orthogonalize the continuum molecular orbitals among them-
selves and remove linearly dependent functions [18,27]. In
A. Theory
general and in this work, all calculations are performed
In an R-matrix approach [23,24], the configuration space within the fixed-nuclei approximation. This is based on the
of the scattering system is divided into two spatial regions: an assumption in which electronic, vibrational, and rotational
inner region and an outer region. These regions are treated motions are uncoupled.
differently in accordance with the different interactions in In the inner region, the wave function of the scattering
each region. The center of the R-matrix sphere coincides system, consisting of target plus scattering electron, is written
with the center of mass of the molecule. When the scattering using the CI expression:
electron leaves the inner region, the other target electrons are


confined to the inner region. In the present work, the R-matrix kN+1 = A φiN (x1 , . . . , xN ) ξj (xN+1 )aij k
boundary radius dividing the two regions was chosen to be i j
10 a0 , centered at the PH center of mass. This sphere encloses

the entire charge cloud of the occupied and virtual molecular + χm (x1 , . . . , xN , xN+1 )bmk , (1)
m
orbitals included in the calculation. At 10 a0 , the amplitudes
−3/2
of the molecular orbitals are less than 10−5 a0 . However, where A is an antisymmetrization operator, xN is the spatial
the continuum orbitals have finite amplitudes at the boundary. and spin coordinates of the N th electron, φiN represents the
Inside the R-matrix sphere, the electron-electron correlation ith state of the N -electron target, ξj is a continuum orbital
and exchange interactions are strong. Short-range correlation spin-coupled with the scattering electron, and k refers to
effects are important for accurate prediction of large-angle a particular R-matrix basis function. Coefficients aij k and
elastic scattering, and exchange effects are important for spin- bmk are variational parameters determined as a result of
forbidden excitation cross sections. A multicentered CI wave the matrix diagonalization. To obtain reliable results, it is
function expansion is used in the inner region. The calculation important to maintain a balance between the N -electron target
in the inner region is similar to a bound-state calculation, representation, φiN , and the (N + 1) electron-scattering wave
which involves the solution of an eigenvalue problem for function. The summation in the second term of Eq. (1) runs

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ELECTRON-IMPACT STUDY OF THE PH RADICAL USING . . . PHYSICAL REVIEW A 81, 022709 (2010)

TABLE I. Properties of the PH target, ground-state energy, and dipole moment (in a.u.) and the
ionization potential (IP, in eV) at bond length Re = 2.687a0 .

Present Previous Theory

Parameter SCF CI SCFa CEPAa SCFb

E −341.26042 −341.29504 −341.28751 −341.42404 −341.2932

µ 0.2521 0.2645 0.2059 0.1876
IP 10.26 10.26 9.63 10.04 9.65
a
Meyer and Rosmus [9].
b
Cade and Huo [3].

over configurations χm , where all electrons are placed in including the continuum electron basis functions centered at
target-occupied and virtual molecular orbitals. The choice of the origin. The VEA is equal to the difference between total
appropriate χm is crucial in this [28]. These are known as energy of the neutral molecule and its anion at the equilibrium
L2 configurations and are needed to account for orthogonality geometry of the neutral molecule. We detect a stable bound
relaxation and for correlation effects arising from virtual state of PH− with 2  symmetry having the configuration
excitation to higher electronic states that are excluded in 1σ 2 2σ 2 1π 4 3σ 2 4σ 2 5σ 2 2π 3 with a VEA value of 0.974 eV,
the first expansion. The basis for the continuum electron is which is in good agreement with the estimated experimental
parametrically dependent on the R-matrix radius and provides (adiabatic) value of about 1.0 eV [31].
a good approximation to an equivalent basis of orthonormal To provide additional information on the charge distribution
spherical Bessel functions [29]. In one-state CI model, we have in the PH molecule, we also calculated the dipole and
included the ground state only but have used the CI wave func- quadrupole moments. In our CI model, the dipole moment
tion to describe it. In the thirty-seven-state model calculation, and the absolute values of quadrupole component Q20 for
each target state is represented by a CI wave function. the ground state are 0.2645 and 0.1316 a.u., respectively. The
values of the ground-state energy, the dipole moment, and the
ionization potential are compared with those from other work
B. PH target model
in Table I.
The molecule PH is a linear open-shell system that has The polarizability tensor gives a good indication of how
ground state X 3  − in the C∞v point group, which is reduced well the polarization interaction will be modeled in the outer
to the C2v point group when the symmetry is lowered. In region. In the present work, the diagonal components αxx ,
the R-matrix suite of programs, the highest Abelian group is αyy , and αzz were computed using second-order perturbation
D2h , and therefore we work in the C2v point group, which theory. These values are αxx = 14.197a03 , αyy = 14.197a03 ,
is a subset of the D2h point group. The results are reported and αzz = 20.489a03 , giving the mean spherical polarizability,
in the natural symmetry point group as well as in the C2v α0 , a value of 16.29 a03 . This is fairly close to the exact
point group for the sake of convenience. We used a double-ζ polarizability value of 16.92a03 reported in the Computational
plus polarization (DZP) Gaussian basis set [30] contracted Chemistry Comparison and Benchmark database.
as (12,8,1)/(6,4,1) for P and (4,2)/(1,1) for H. We avoided In Table II, we list the dominant configuration, the transition
using diffuse functions as these would extend outside the moments, N [the number of configuration state functions
R-matrix box. We first performed an Self-consistent Field (CSFs)], and the vertical excitation energies for the target
(SCF) calculation for the ground state of the PH molecule states. We have good agreement with the full CI calculation
with the chosen DZP basis set and obtained a set of occupied of Bruna et al. [4]. It is difficult to achieve the same degree
and virtual set of orbitals. of accuracy using only a single set of molecular orbitals to
The Hartree-Fock electronic configuration for the ground describe all the target states. Our R-matrix formalism as coded
state is 1σ 2 2σ 2 3σ 2 1π 4 4σ 2 5σ 2 2π 2 . The energy of occupied in the suite of R-matrix programs restricts us to only the single
2π orbital is −10.26 eV, and by the Koopman theorem the first set of one-particle orbitals. The reference state chosen with this
ionization energy is 10.26 eV, which is in reasonable agreement single set of SCF orbitals is the ground state of the molecule.
with the experimental value of 10.17 eV [14]. Because the
SCF procedure is inadequate to provide a good representation
of the target states, we improve the energy of the ground as C. Scattering model
well as the excited states by using CI wave functions. This We have included thirty-seven target states (four of 1 A2 ,
lowers the energies, and the correlation introduced provides a six of 3 A2 , six of 1 A1 , three of 3 A1 , four of 1 B1 , five
better description of the target wave function and excitation of 3 B1 , four of 1 B2 , and five of 3 B2 ) in the trial wave
energies. In our limited CI model, we keep ten electrons frozen function describing the electron-plus-target system. However,
in the 1σ 2 2σ 2 3σ 2 1π 4 configuration and allow the remaining excitation cross sections are reported only for the four excited
six electrons to move freely in molecular orbitals 4σ , 5σ , 6σ , states (a 1 , b 1  + , A 3 , and c 3 ) that are below the
7σ , 8σ , 2π, and 3π . The CI ground-state energy for a PH first ionization threshold. Calculations were performed for
molecule is −341.295043 Hartrees, at a bond length of Re = doublet and quartet scattering states with A1 , A2 , B1 , and B2
2.687 a0 . We computed the value of vertical electronic affinity symmetries. Continuum orbitals up to l = 4 (g partial wave)
(VEA) by performing a bound-state calculation of PH− by were included in the scattering calculation.

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JASMEET SINGH RAJVANSHI AND K. L. BALUJA PHYSICAL REVIEW A 81, 022709 (2010)

TABLE II. Dominant configuration, transition moments (in a.u.), N (the number of CSFs), and the vertical excitation
energies (VEE, in eV) for the target states of PH at bond length Re = 2.687 a0 .

State Dominant Transition VEE

C2v /C∞v configuration moments N This work Full CIa

X 3 A2 /X 3  − 1σ 2 2σ 2 3σ 2 4σ 2 5σ 2 1π 4 2π 2 0.2645b 864 0.000 0.000

a (1 A2 ,1 A1 )/a 1  1σ 2 2σ 2 3σ 2 4σ 2 5σ 2 1π 4 2π 2 – 584, 696 1.38 1.12
b (1 A1 )/b 1  + 1σ 2 2σ 2 3σ 2 4σ 2 5σ 2 1π 4 2π 2 – 696 1.98 1.98
A 3 B1 , 3B2 /A 3  1σ 2 2σ 2 3σ 2 4σ 2 5σ 1π 4 2π 3 0.5616 858 4.03 3.86
c 1 B2 , 1B1 /c 1  1σ 2 2σ 2 3σ 2 4σ 2 5σ 1π 4 2π 3 – 620 5.47 5.02
a
Bruna et al. [4].
b
Dipole moment.

Because of the presence of the long-range dipole interac- center of mass of the molecule. The potential energy curves of
tion, the elastic cross sections are formally divergent in the the 3  − state of the PH molecule and the 2  state of the PH−
fixed-nuclei approximation as the differential cross section is anion are shown in Fig. 1. The anion is stable at all the bond
singular in the forward direction. To obtain converged cross lengths. This yields a VEA of 0.974 eV at Re . From Fig. 1,
sections, the effect of rotation must be included along with we find that the equilibrium bond length for the ground state
a very large number of partial waves. The effects of partial of the anion PH− is 2.72 a0 , which is in excellent agreement
waves with l > 4 were included using a Born correction via with the theoretical value 2.71 a0 obtained by an ab initio
a closure approach [32]. Our partial g-wave cross section calculation [13]. The PH bond length is about 1.2% elongated
using R-matrix method nearly coincided with the g-wave Born in the anionic state PH− because the extra electron is in a ∗
results. This establishes the correctness of our procedure to use orbital. Our value of adiabatic electron affinity is 0.974 eV,
Born correction beyond the g-partial wave. which is in good agreement with the estimated experimental
(adiabatic) value of about 1.0 eV [31] and also comparable with
III. RESULTS
the theoretical value, 1.013 eV [14]. The dissociation energy,
De , for the PH− molecule is 3.011 eV. The dissociation energy,
The ground-state electronic configuration of PH has two De , for the PH molecule is 2.7 eV, which is comparable with
unpaired π electrons. Because of vacancy in 2π orbital of the values 2.9 [9] and 3.1 eV in other work [15].
the ground state of PH, the scattering electron can occupy it, In Fig. 2, we have summed the contribution of doublet and
forming a stable anionic ground state of PH with symmetry quartet symmetries for one-state CI calculations. In this figure,
2
. In our thirty-seven-state model, we found an R-matrix we show the elastic cross section calculated by including only
pole at −341.33083 a.u. at Re in the scattering symmetry 2 , the ground state, which is correlated, where the active space
which is less than the energy −341.29504 a.u. of ground state spans orbitals up to 8σ and 3π . We notice two peaks in the
X3  − of PH, which indicates the detection of an anionic bound cross sections at 6.75 and 7.9 eV. The eigenphase sum shows a
state. We calculated the bound-state energies of this anionic sudden jump of π rad centered at these positions. In the context
2
 state at different bond lengths by performing an L2 -type of the one-state model, these are considered pseudoresonances.
calculation in which we placed the scattering electron at the These resonances belong to degenerate (2 A1 /2 A2 )2  symme-
try and (4 B1 /4 B2 )4  symmetry, respectively. To investigate

4 150

3 - Total (1-state CI)

Σ PH
2 - 140
3 Π PH
Elastic cross section (units of a0 )
2

130
Energy (units of eV)

2
120

1 110

100
0

90

-1
80
0 1 2 3 4 5 6 7 8 9 10
2 3 4 5 6 Energy (units of eV)
Bond length (units of a0)
FIG. 2. Elastic cross sections of the electron impact on the
FIG. 1. Ground-state potential energy curves of PH and PH molecule at a bond length Re = 2.687 a0 for one-state CI
PH− molecules. Dashed curve, PH; solid curve, PH− . calculations.

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ELECTRON-IMPACT STUDY OF THE PH RADICAL USING . . . PHYSICAL REVIEW A 81, 022709 (2010)

4
Doublets
3 3 3
150 Quartets X A2 --> A B1 / A B2
Total (Doublets + Quartets) Doublets
Quartets
Born correction
Born corrected Total (37-state)

Excitation cross sections (units of ao )

Elastic cross sections (units of a0 )

125

2
2

3 Born correction
Born corrected

100

75 2

50

1
25

0
0 1 2 3 4 5 6 7 8 9 10 0
Energy (units of eV) 3 4 5 6 7 8 9 10
Energy (units of eV)
FIG. 3. Elastic cross sections of the electron impact on the
PH molecule at Re for thirty-seven-state calculations. Dashed curve, FIG. 4. Electron-impact excitation cross sections from the ground
doublets sum, dash-dotted curve, quartets sum; thin soild line, total X 3  − (3 A2 ) state of the PH molecule to the A 3  (3 B1 /3 B2 ) state
(doublets + quartets); dotted curve, Born correction; and thick solid for the thirty-seven-state calculation. Dashed curve, doublets sum;
line, Born corrected. Born corrected is the sum of Doublets, Quartets dash-dotted curve, quartets sum; thin solid line, total; dotted curve,
and Born correction. Born correction; and thick solid line, Born corrected. Born corrected
is the sum of Doublets, Quartets and Born correction.
whether these resonances are real, we performed calculations excited states that lie below the vertical ionization potential
in a thirty-seven-state model in which the last target threshold are shown in Figs. 3, 4, and 5. The states above the vertical
was 16.86 eV. The pseudoresonances seen in the one-state ionization potential are included to improve the modeling of
CI model are washed out in this thirty-seven-state model as a the polarization potential. The ionization potential of the PH
result of the inclusion of higher excited states. state is 10.26 eV; therefore, we report all the excitation cross
In Fig. 3, we present the elastic cross sections of the electron sections up to 10 eV. The retention of a large number of
impact on the PH molecule at Re for the thirty-seven-state closed electronic excitation channels provides the necessary
calculation. We show the contributions of doublet and quartet polarization potential in an ab initio way. This polarization
symmetries separately. There is a steep rise in the cross section potential is critical in determining the resonance parameters
as we lower the energy to less than 1 eV. This effect is due of the detected resonances. In Figs. 4 and 5, we show the
to the long-range dipole moment of the molecule. The rise in inelastic cross sections from the ground state to the first four
cross section for the quartet symmetries beyond 1 eV up to physical states whose vertical excitation thresholds, dominant
4 eV is due to the contribution of 4 A2 symmetry. Beyond 4 eV, configuration, and the number of CSFs included in the CI
the cross section for the quartet symmetries is nearly constant. expansion, which are given in Table II.
For the doublet symmetries, there is a mild dependence of the Figure 4 depicts the excitation cross section for the opti-
cross section on the energy in the range 1 to 10 eV. The Born cally allowed transition X 3 A2 (X 3  − )–A 3 B1 /3 B2 (A 3 ).
correction shown in the figure is added to the sum of doublets The contribution of quartet and doublet symmetries is shown
and quartets to get elastic cross section, which includes separately. The contribution of quartets is more than that of
contribution of partial waves. The Born correction accounts
for contribution of cross sections from partial waves greater 1.5
than l = 4. To achieve this, we have subtracted the contribution 3
X A2 --> a A2 / a A1
1 1

of partial Born cross sections from the corresponding R-matrix 3

X A2 --> b A1
1

values and added the full Born cross section. Ideally, one 3
X A2 --> c B2 / c B1
1 1
Excitation cross sections (units of a0 )
2

should use this procedure at the scattering amplitude level

1
to avoid getting unphysical negative cross sections. If caution
is exercised, then the correction at the cross-section level is
computationally more convenient. For partial waves greater
than l = 4, there is no need to use an antisymmetrized Born
wave function because the centrifugal barrier is high and the 0.5
effect of exchange is negligible. The contribution from higher
partial waves to the cross section arises from distort collisions
and is dominated by the electron-dipole interaction. It can
be estimated in the Born approximation. In fact, our R-matrix
0
cross section result for the g-partial wave is in close agreement 1 2 3 4 5 6
Energy (units of eV)
7 8 9 10

with the Born result, thus justifying the use of the Born closure
procedure at the cross-section level. FIG. 5. Electron-impact excitation cross sections from the ground
Our calculation has included thirty-seven target states, X 3  − (3 A2 ) state of the PH molecule to a 1  (1 A2 /1 A1 ), thin solid
out of which only the ground state and the four low-lying curve; b 1  + (1 A1 ), dashed curve; and c 1  (1 B2 /1 B1 ), dotted curve.

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7 TABLE III. PH molecular orbital binding and average kinetic

energies for DZP basis set at equilibrium geometry. |B| is binding
6 energy (eV), U is kinetic energy (eV), and N is occupation number.
Ionization cross section (units of 10 cm )
2
-16

5 Molecular orbital |B| (eV) U (eV) N

1σ (1a1 ) 2175.89 2889.72 2

4
2σ (2a1 ) 204.18 431.62 2
3σ (3a1 ) 146.75 401.95 2
3
4σ (4a1 ) 21.00 43.80 2
5σ (5a1 ) 12.34 34.92 2
2
1π (1b1 ) 146.75 401.71 2
1π (1b2 ) 146.75 401.71 2
1
2π (2b1 ) 5.13 36.60 1
2π (2b2 ) 5.13 36.60 1
0
10 100 1000
Electron Energy (units of eV)
     
s 1 1 1 lnt
FIG. 6. Electron impact BEB ionization cross sections of the PH σi (t) = 1 − 2 lnt + 1 − − ,
molecule. t +u+1 2 t t t +1
(2)
doublet symmetries as a result of their higher spin multiplicity in which t = T /B, u = U/B, and s = 4π a0 2 N (R/B)2 . Here,
(by a factor of two) than that of doublet symmetries. The peak R is the Rydberg energy, T is the kinetic energy of the incident
in the cross section around 6.1 eV is due to 4 B2 symmetry. This electron, U is the orbital kinetic energy, N is the electron
is due to a weak resonance, as detected in the eigenphase sum occupation number, and B is the binding energy of the orbital.
analysis. The eigenphase sum increases by 1.5 rad in a small The evaluation of the differential cross sections (DCS)
energy range around this peak. Its width is approximately 1.0 provides a more stringent test for any theoretical model.
eV. This weak resonance is not seen in the elastic cross section Besides this, the data on DCS are used to calculate the
because of much larger cross sections with respect to inelastic momentum-transfer cross section (MTCS) that shows the
cross sections. We assigned a configuration 5σ 2π 3 6σ to this importance of backward-angle scattering. We have calculated
core excited shape resonance, which decays to the parent state the DCS using the POLYDCS program of Sanna and Gianturco
(5σ 2π 3 )A 3  by dissociating a 6σ molecular orbital. The [33], which requires basic molecular input parameters along
Born correction, which increases with increase in energy, is with K matrices evaluated in a particular scattering calculation.
shown, and at 10 eV, its contribution is almost 20%. We have used this code to compute the DCS in the one-state CI
Figure 5 shows the excitation cross section for the ground model. The DCS for elastic electron PH scattering is given by
state to the singlet excited states a 1 , b 1  + , and c 1 .      
These transitions are spin-forbidden. The cross section for the dσ 1 dσ Q dσ D
= 2 + , (3)
a 1  state rises linearly with energy from its threshold to d 3 d d
2.5 eV, peaks around 5 eV, and then decreases. The kinks seen
in the cross sections are the excitation thresholds of the higher where ( ddσ )Q,D represents the DCS for quartet and doublet
excited states. The cross section curve for the b 1  + state cases, respectively.
shows a rapid rise from threshold up to the excitation threshold Figure 7 displays our calculated differential cross section
of A 3  state at 4 eV, beyond which it remains nearly constant for electron scattering by the ground state of PH at incident
at 0.5 a0 2 . The cross section for the last excited state c 1 , energies of 1, 3, 5, 7, and 10 eV in the one-state CI model at
shown in Fig. 5, has a smaller cross section with respect to the Re . The steep rise of DCS in the forward direction is typical for
excitation cross section of other singlet states because of its scattering of electrons from a polar molecule. We note that as
much greater threshold value, 5.47 eV. energy increases, the DCS in the backward direction increases
Figure 6 shows the electron-impact ionization cross section up to 5 eV and then begins to decrease. This behavior is clearly
of PH from threshold 10.26 to 5,000 eV using the standard for- reflected in the MTCS, shown in Fig. 8.
malism of the BEB model [21,22]. This formalism requires the Because the DCS is not very sensitive to correlation effects
binding energy and kinetic energy of each occupied orbital in for backward scattering, we expect our MTCS to be quite
a molecular structure calculation. The ionization cross section reliable in the 0.01–10 eV range. These are calculated in
rises from threshold to a peak value of 6.63 Å2 at 47.34 eV the one-state CI model. MTCS provides a useful input in
and then shows ln E/E behavior as E approaches greater solving the Boltzmann equation for the electron distribution
values. In the absence of any other calculations on ionization function. In contrast to the diverging nature of DCS in the
cross sections of PH by electron impact, our data provide a forward direction, MTCS show no singularity due to the
useful resource to the applied and theoretical communities. weighting factor (1 − cosθ ), where θ is scattering angle.
The molecular orbital data used in the calculation of the BEB This factor vanishes as θ → 0. The MTCS is useful in the
cross section is given in Table III, which is generated at the study of electrons drifting through a molecular gas. When
SCF level. The BEB ionization cross section σ is obtained by a swarm of electrons travels through a molecular gas under
summing over each orbital cross section σi , where the influence of an electric field, several transport observables

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ELECTRON-IMPACT STUDY OF THE PH RADICAL USING . . . PHYSICAL REVIEW A 81, 022709 (2010)

100 100

Differential cross section (units of 10 cm /str) 1 eV 3 eV

Differential cross section (units of 10 cm /str)

2

2
-16

-16
10 10

1 1

0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120 140 160 180
Scattering angle (deg) Scattering angle (deg)

5 eV
Differential cross section (units of 10 cm /str)
2
-16

10

0 20 40 60 80 100 120 140 160 180

Scattering angle (deg)

7 eV
Differential cross section (units of 10 cm /str)
2
-16

10

0 20 40 60 80 100 120 140 160 180

Scattering angle (deg)

10 eV
Differential cross section (units of 10 cm /str)
2
-16

10

0 20 40 60 80 100 120 140 160 180

Scattering angle (deg)

FIG. 7. Differential cross sections at 1, 3, 5, 7, and 10 eV for the one-state CI model at Re .

like diffusion coefficient D and mobility µ can be obtained It is minimal around 1 eV and then rises up to its peak
if we have a knowledge of the MTCS. From Fig.8, we value of 22.3 Å2 at 4.8 eV, beyond which it gradually
observe that MTCS decreases sharply with increasing energy. decreases.

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JASMEET SINGH RAJVANSHI AND K. L. BALUJA PHYSICAL REVIEW A 81, 022709 (2010)

Elastic, (integrated and differential) momentum transfer, exci-

cm )

tation, and ionization cross sections have been presented. The

2

24
results of the one-state CI and thirty-seven-state close-coupling
-16
Momentum transfer cross sections (units of 10

approximation are presented. We detect a stable bound state of

22 PH− having configuration 1σ 2 2σ 2 3σ 2 4σ 2 1π 4 5σ 2 2π 3 with a
vertical electronic affinity value of 0.974 eV, which is in good
agreement with the estimated experimental value of about
20 1.0 eV. The target states are represented by including cor-
relations via a CI technique. Our target calculations give
reasonable agreement with the calculated vertical excitation
18 spectrum of Bruna et al. [4]. We hope that the results presented
here will not only be useful for comparison with future
experimental studies but will also provide data useful in plasma
16
0 1 2 3 4 5 6 7 8 9 10
modeling, though lack of any experimental or other theoretical
Energy (units of eV) data makes it difficult to benchmark this study for open-shell
molecules.
FIG. 8. MTCS at different energies for Re = 2.687 a0 of PH
molecule ground state at the one-state CI level.
ACKNOWLEDGMENTS
IV. CONCLUSIONS
This work was financially supported by Council of Sci-
This is a comprehensive ab initio study of electron impact entific and Industrial Research (CSIR), India, under Grant
on the PH molecule using the UK molecular R-matrix codes. No. F. NO. 09/045(0757)/2008-EMR-I.

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