Imperial College London
Alternate

Professor Mike Robb, FRS

Faculty of Natural Sciences, Department of Chemistry

Chair in Chemistry
 
 
 
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Contact

 

+44 (0)20 7594 5757mike.robb Website

 
 
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Location

 

301cMolecular Sciences Research HubWhite City Campus

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Summary

 

Publications

Citation

BibTex format

@article{Santolini:2015:10.1080/00268976.2015.1025880,
author = {Santolini, V and Malhado, JP and Robb, MA and Garavelli, M and Bearpark, MJ},
doi = {10.1080/00268976.2015.1025880},
journal = {Molecular Physics},
pages = {1978--1990},
title = {Photochemical reaction paths of cis-dienes studied with RASSCF: the changing balance between ionic and covalent excited states},
url = {http://dx.doi.org/10.1080/00268976.2015.1025880},
volume = {113},
year = {2015}
}
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RIS format (EndNote, RefMan)

TY  - JOUR
AB  - The balanced description of ionic and covalent molecular excited electronic states still presents a challenge for currentelectronic structure methods. In this contribution, we show how the restricted active space self-consistent field (RASSCF)method can be used to address this problem, applied to two dienes in the cis conformation. As with the closely relatedcomplete active space self-consistent field (CASSCF) method, the construction of the orbital active space in the RASSCFmethodology requires the a priori formulation of a physical or theoretical model of the system being studied. In this article,we discuss how the active space can be constructed in a guided and systematic way, using pairs of natural bond orbitalsas correlating partner orbitals (oscillator orbitals) and semi-internal correlation. The resulting balanced description of thecovalent and ionic valence excited states – with the ionic state correctly lower in energy at the Franck–Condon geometry –is suitable to study the photochemistry of these and other molecules.
AU  - Santolini,V
AU  - Malhado,JP
AU  - Robb,MA
AU  - Garavelli,M
AU  - Bearpark,MJ
DO  - 10.1080/00268976.2015.1025880
EP  - 1990
PY  - 2015///
SN  - 1362-3028
SP  - 1978
TI  - Photochemical reaction paths of cis-dienes studied with RASSCF: the changing balance between ionic and covalent excited states
T2  - Molecular Physics
UR  - http://dx.doi.org/10.1080/00268976.2015.1025880
UR  - http://hdl.handle.net/10044/1/30746
VL  - 113
ER  -
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