Modeling solvent effects on electron spin resonance hyperfine couplings by frozen-density embedding

Neugebauer, Johannes; Louwerse, Manuel J.; Belanzoni, Paola; Wesolowski, Tomasz Adam; Baerends, Evert Jan

doi:10.1063/1.2033749

Scientific article

English

Modeling solvent effects on electron spin resonance hyperfine couplings by frozen-density embedding

Contributors

Neugebauer, Johannes; Louwerse, Manuel J.; Belanzoni, Paola; Wesolowski, Tomasz Adam; Baerends, Evert Jan

Published in

The Journal of chemical physics, vol. 123, no. 41, 114101

Publication date

2005

Abstract

In this study, we investigate the performance of the frozen-density embedding scheme within density-functional theory [J. Phys. Chem. 97, 8050 (1993)] to model the solvent effects on the electron-spin-resonance hyperfine coupling constants (hfcc's) of the H2NO molecule. The hfcc's for this molecule depend critically on the out-of-plane bending angle of the NO bond from the molecular plane. Therefore, solvent effects can have an influence on both the electronic structure for a given configuration of solute and solvent molecules and on the probability for different solute (plus solvent) structures compared to the gas phase. For an accurate modeling of dynamic effects in solution, we employ the Car-Parrinello molecular-dynamics (CPMD) approach. A first-principles-based Monte Carlo scheme is used for the gas-phase simulation, in order to avoid problems in the thermal equilibration for this small molecule. Calculations of small H2NO-water clusters show that microsolvation effects of water molecules due to hydrogen bonding can be reproduced by frozen-density embedding calculations. Even simple sum-of-molecular-densities approaches for the frozen density lead to good results. This allows us to include also bulk solvent effects by performing frozen-density calculations with many explicit water molecules for snapshots from the CPMD simulation. The electronic effect of the solvent at a given structure is reproduced by the frozen-density embedding. Dynamic structural effects in solution are found to be similar to the gas phase. But the small differences in the average structures still induce significant changes in the computed shifts due to the strong dependence of the hyperfine coupling constants on the out-of-plane bending angle.

UNIGE affiliation entities

Faculté des sciences / Section de chimie et biochimie / Département de chimie physique

UNIGE research groups

Groupe Wesolowski

Citation (ISO format)

NEUGEBAUER, Johannes et al. Modeling solvent effects on electron spin resonance hyperfine couplings by frozen-density embedding. In: The Journal of chemical physics, 2005, vol. 123, n° 41, p. 114101. doi: 10.1063/1.2033749

Article (Published version)

Identifiers

PID : unige:3619
DOI : 10.1063/1.2033749

Journal ISSN

0021-9606

637views

667downloads

Creation

02/10/2009 15:18:59

First validation

02/10/2009 15:18:59

Update

14/03/2023 15:15:41

Status update

14/03/2023 15:15:40

Last indexation

10/06/2025 21:31:00

Modeling solvent effects on electron spin resonance hyperfine couplings by frozen-density embedding

Contributors

Published in

Publication date

Abstract

UNIGE affiliation entities

UNIGE research groups

Citation (ISO format)

Main files (1)

Identifiers

Journal ISSN

Technical informations

Creation

First validation

Update

Status update

Last indexation