A state-specific polarizable continuum model time dependent density functional theory method for excited state calculations in solution

Improta, Roberto; Barone, Vincenzo; Scalmani, Giovanni; Frisch, Michael J.

doi:doi:10.1063/1.2222364

Volume/Page
Keyword
DOI
Citation
Advanced

Volume: Page/Article:

Search Content Type

article doi:

Citation:

Coordinate transformation methods to calculate state-to-state reaction probabilities with wave packet treatments

A procedure for the transformation from reactant to product Jacobi coordinates is proposed, which is designed for the extraction of state-to-state reaction probabilities using a time-dependent method in a body-fixed frame. The method consists of several steps which involve a negligible extra computational time as compared with the propagation. Several intermediate coordinates are used, in which the efficiency depends on the masses of the atoms involved in the reaction. A detailed study of the r...

Statistical estimates of electron correlations

While arbitrarily accurate solutions to the many-body Schrödinger equation are possible through a brute force expansion of the wave function, the length of the expansions required renders the approach intractable except for few-electron problems. By considering the form of the energy resulting from truncation of the many-particle expansion space, it is shown that accurate determination of electron correlations may be extracted from estimates of average or effective energy contributions while ma...

An effective state specific (SS) model for the inclusion of solvent effects in time dependent density functional theory (TD-DFT) computations of excited electronic states has been developed and coded in the framework of the so-called polarizable continuum model (PCM). Different relaxation time regimes can be treated thus giving access to a number of different spectroscopic properties together with solvent relaxation energies of paramount relevance in electron transfer processes. SS and conventional linear response (LR) models have been compared for two benchmark systems (coumarin 153 and formaldehyde in different solvents) and in the limiting simple case of a dipolar solute embedded in a spherical cavity. The results point out the complementarity of LR and SS approaches and the advantages of the latter model especially for polar solvents. The favorable scaling properties of PCM-TD-DFT models in both SS and LR variants and their availability in effective quantum mechanical codes pave the route for the computation of reliable spectroscopic properties of large molecules of technological and/or biological interest in their natural environments.

Article Outline

INTRODUCTION
THEORETICAL METHODOLOGY
1. Computational details
RESULTS
1. Coumarin 153
2. Formaldehyde
DISCUSSION
CONCLUDING REMARKS

RELATED DATABASES

To view database links for this article, you need to log in.

KEYWORDS and PACS

Keywords

excited states, solvent effects, density functional theory, organic compounds

PACS

31.50.Df

Potential energy surfaces for excited electronic states
31.70.Dk

Environmental and solvent effects
31.15.E-

Density-functional theory

ARTICLE DATA

Digital Object Identifier

http://dx.doi.org/10.1063/1.2222364

PUBLICATION DATA

ISSN

0021-9606 (print)

1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef

American Institute of Physics

For access to citing articles, you need to log in.

Figures (2) Tables (2)

Access to article objects (figures, tables, multimedia) requires a subscription; log in to view available files.
(Access to supplementary files, where available, is free for this journal.)