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CASSCF calculations for photoinduced processes in large molecules: Choosing when to use the RASSCF, ONIOM and MMVB approximations

Paper ID Volume ID Publish Year Pages File Format Full-Text
28088 44059 2007 21 PDF Available
Title
CASSCF calculations for photoinduced processes in large molecules: Choosing when to use the RASSCF, ONIOM and MMVB approximations
Abstract

In this article, we compare and contrast the RASSCF, ONIOM and MMVB electronic structure methods for calculating relaxation paths on potential energy surfaces of the excited states of large molecules, and for locating any resulting conical intersections at which nonadiabatic decay can take place. Each method is treated here as an approximation to CASSCF, which we choose as our reference level of theory, but which becomes prohibitively expensive computationally for large molecules. Both MMVB and ONIOM are hybrid computational methods – combining different levels of theory in an energy plus derivatives calculation at a particular molecular geometry – but they differ fundamentally in that MMVB is a hybrid-atom method, whereas ONIOM is a hybrid-molecule method. We explain this distinction through four representative applications: the photostability of pyracylene (studied with CASSCF, RASSCF, MMVB); large geometry changes in the singlet excited states of triangulene (studied with MMVB); a model for interstitial nickel defects in a synthetic diamond lattice (studied with ONIOM CAS:UFF); and the photochemical [4 + 4] cycloaddition of cyclohexadiene to naphthalene (studied with ONIOM CAS:MMVB). We show that each method is more appropriate for a particular type of photochemical problem. This article is part perspective, part review, and contains new results for three multi-state or photoinduced processes in complex systems.

Keywords
CASSCF; RASSCF; ONIOM; MMVB; Excited states; Hybrid method; QM/MM; Pyracylene; Triangulene; Diamond defect; Photochemical cycloaddition
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CASSCF calculations for photoinduced processes in large molecules: Choosing when to use the RASSCF, ONIOM and MMVB approximations
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Publisher
Database: Elsevier - ScienceDirect
Journal: Journal of Photochemistry and Photobiology A: Chemistry - Volume 190, Issues 2–3, 15 August 2007, Pages 207–227
Authors
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Subjects
Physical Sciences and Engineering Chemical Engineering Bioengineering
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Don't Miss Today's Special Offer
Price was $35.95
You save - $31
Price after discount Only $4.95
100% Money Back Guarantee
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