Lecture 33
Calculation of Thermodynamic Properties
Thermodynamics and Kinetics of a Reaction
A+B→C+D
ΔG°, ΔH°, ΔS°
ΔG‡, ΔH‡, ΔS‡
∆G° = –RTlnKeq
k = (kBT/h)exp(–∆G‡/RT)
Thermodynamic vs. Kinetic Control
Thermodynamics, ΔG° (feasibility of a reaction)
Kinetics, ΔG‡ (speed of a reaction) P1: Thermodynamic Control
P2: Kinetic Control
Calculation of Thermodynamic Parameters
How do we compute Thermodynamic Properties from Computational Quantum Chemistry?
…we have (vibrationally corrected) energy of one molecule!
Enthalpy (H)
Canonical Ensemble Entropy (S)
(N,V,T) Gibbs Free Energy (G)
Thermodynamic properties are valid for a large number of molecules, not individual molecules!
Quantum Mechanics of Thermodynamic
Statistical Mechanics
individual molecules Properties
Use quantum mechanics to compute molecular partition functions (q), obtain thermodynamic
properties from the partition functions in the usual way
Partition Function
Partition Function (of a System)
(The statistical mechanical analogue of wave function in quantum mechanics)
"#$#%"
𝑄 𝑁, 𝑉, 𝑇 = ' 𝑒 &'! (),+)/." /
!
i runs over all possible energy states of the system having energy Ei
Ideal Gas Assumption (indistinguishable molecules)
0%1%0"
)
𝑞(𝑉, 𝑇)
𝑄 𝑁, 𝑉, 𝑇 = 𝑞 𝑉, 𝑇 = ' 𝑔. 𝑒 &2# /." /
𝑁!
.
Total Per Molecules
Separability of Energy Components
𝑞 𝑉, 𝑇 = 𝑞%0%3 (𝑇) . 𝑞#4$5" (𝑉, 𝑇) . 𝑞46# (𝑇) . 𝑞1!7 (𝑇)
Molecular energy 𝜀 can be separated as a sum of electronic, translational, rotational, and vibrational terms
Partition Function
Contribution due to electronic motion
𝑞%0%3 (𝑇) = 𝑔8 𝑒 &9$ /." / + 𝑔: 𝑒 &9% /." / + 𝑔; 𝑒 &9& /." / + ⋯
𝑞%0%3 (𝑇) = 𝑔8
Ground-state energy is set to zero, and excited states are inaccessible; g is electronic degeneracy
Contribution due to translational motion
=/;
2𝜋𝑚𝑘< 𝑇 𝑘< 𝑇
𝑞#4$5" (𝑉, 𝑇) =
ℎ; 𝑃
Contribution due to rotational motion
:/; =/;
𝜋𝐼> 𝐼< 𝐼? 8𝜋 ; 𝑘< 𝑇
𝑞46# 𝑇 =
𝜎4 ℎ;
Contribution due to vibrational motion (QMHO)
=)&A
1 𝜔! vibrational frequency of
𝑞1!7 𝑇 = ;
1 − 𝑒 &BC! /." / the ith normal mode
!@:
Thermodynamic Properties
Inner Thermal Energy (U)
𝜕 ln 𝑞
𝑈 = 𝑁𝑘< 𝑇 ;
𝜕𝑇 ),+
Enthalpy (H)
𝜕 ln 𝑞 𝜕 ln 𝑞
𝐻 = 𝑈 + 𝑃𝑉 = 𝑁𝑘< 𝑇 ; + 𝑁𝑘< 𝑇 𝑉
𝜕𝑇 ),+ 𝜕𝑉 /
Entropy (S)
𝜕 ln 𝑞
𝑆 = 𝑁𝑘< 𝑇 + 𝑁𝑘< ln 𝑞
𝜕𝑇 ),+
Gibbs Free Energy (G)
𝜕 ln 𝑞
𝐺 = 𝐻 − 𝑇𝑆 = 𝑁𝑘< 𝑇 𝑉 − 𝑁𝑘< 𝑇 ln 𝑞
𝜕𝑉 /
Thermodynamic Calculation in ORCA
Assumptions
T = 298.15 K
P = 1 atm Output from frequency
Ideal gas calculation
RRHO Approximation
Electronically nondegenerate
No excited state is populated
Electronic energy
Zero-Point energy (QM, freq. calc.)
from QM SCF Calc.
𝑈 = 𝐸%0 + 𝐸DE' + 𝐸1!7 + 𝐸46# + 𝐸#4$5" Total Thermal Energy
Thermal corrections from partition functions
Thermodynamic Calculation in ORCA
Output from frequency
calculation
Total thermal energy
𝐻 = 𝑈 + 𝑘< 𝑇
Thermal enthalpy correction
Total Enthalpy
Thermodynamic Calculation in ORCA
The entropy (S) due to each
motion (Selec, Strans, Srot, Svib)
are also computed from
statistical mechanical
equations
Output from frequency
calculation
𝑇 . 𝑆 = 𝑇 . 𝑆%0 + 𝑆#4$5" + 𝑆46# + 𝑆1!7 Total Entropy Term
Entropy contribution due to molecular motions
Thermodynamic Calculation in ORCA
Output from frequency
calculation
Total Enthalpy
𝐺 =𝐻−𝑇.𝑆
Total Entropy Term
Final Gibbs Free Energy
Calculation of Reaction Energetics
A+B→C+D
Reaction exergonicity or endergonicity
∆𝐺 ° = 𝐺? + 𝐺G − 𝐺> + 𝐺<
Activation free energy
∆𝐺 ‡ = 𝐺><‡ − 𝐺> + 𝐺<
Activation energy
∆𝐸 ‡ = 𝐸><‡ − 𝐸> + 𝐸<
Similarly, enthalpy, entropy changes can be computed
Kinetics (rate constants) can be computed using Eyring equation (TST)
𝑘< 𝑇 &∆J ‡ /K/
𝑘= 𝑒
ℎ