Calculation of Reaction Free Energies in Solution: A Comparison of Current Approaches

被引：117

作者：

Besora, Maria ^{[1
]}

Vidossich, Pietro ^{[2
,3
]}

Lledos, Agusti ^{[2
]}

Ujaque, Gregori ^{[2
]}

Maseras, Feliu ^{[1
,2
]}

机构：

[1] Barcelona Inst Sci & Technol, Inst Chem Res Catalonia ICIQ, Avinguda Paisos Catalans 16, Tarragona 43007, Catalonia, Spain

[2] Univ Autonoma Barcelona, Dept Quim, Cerdanyola Del Valles 08193, Catalonia, Spain

[3] Univ Los Andes, Dept Chem, COBO Computat Bioorgan Chem Bogota, Carrera 1 18A 10, Bogota 111711, Colombia

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2018年 / 122卷 / 05期

关键词：

N-HETEROCYCLIC CARBENE; SOLVATION FREE-ENERGIES; BAYLIS-HILLMAN REACTION; GAS-PHASE ENTROPIES; CATALYZED BORYLATION; MOLECULAR-DYNAMICS; OXIDATIVE-ADDITION; OLEFIN METATHESIS; CONTINUUM MODELS; CARBON-DIOXIDE;

D O I：

10.1021/acs.jpca.7b11580

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The result of the application of different approaches based on the ideal gas/rigid rotor/harmonic oscillator (IGRRHO) model, commonly used in popular software packages, for the calculation of free energies in solution is compared with that of ab initio molecular dynamics for a process involving ligand exchange in palladium complexes. The IGRRHO-based approaches considered differ in most cases in the extent to which the rotational and translational contributions are included in the correction. Our study supports the use the free energy values directly obtained from dispersion-corrected DFT functionals without any correction or with minor corrections at most.

引用

页码：1392 / 1399

页数：8

共 105 条

[1] RELATIONSHIP BETWEEN SOLUTION ENTROPIES AND GAS-PHASE ENTROPIES OF NON-ELECTROLYTES [J].