Assessment of MC-PDFT Excitation Energies for a Set of QM/MM Models of Rhodopsins

María Del Carmen Marín, Luca De Vico, Sijia Dong, Laura Gagliardi, Donald G Truhlar, Massimo Olivucci

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Abstract

A methodology for the automatic production of quantum mechanical/molecular mechanical (QM/MM) models of retinal-binding rhodopsin proteins and subsequent prediction of their spectroscopic properties has been proposed recently by some of the authors. The technology employed for the evaluation of the excitation energies is called Automatic Rhodopsin Modeling (ARM), and it involves the use of the complete active space self-consistent field (CASSCF) method followed by a multiconfiguration second-order perturbation theory (in particular, CASPT2) calculation of external correlation energies. Although it was shown that ARM is capable of successfully reproducing and predicting spectroscopic property trends in chromophore-embedding protein sets, practical applications of such technology are limited by the high computational costs of the multiconfiguration perturbation theory calculations. In the present work we benchmark the more affordable multiconfiguration pair-density functional theory (MC-PDFT) method whose accuracy has been recently validated for retinal chromophores in the gas phase, indicating that MC-PDFT could potentially be used to analyze large (e.g., few hundreds) sets of rhodopsin proteins. Here, we test this theory for a set of rhodopsin QM/MM models whose experimental absorption maxima ( a max ) have been measured. The results indicate that MC-PDFT may be employed to calculate a max values for this important class of photoresponsive proteins.

Original languageEnglish (US)
Pages (from-to)1915-1923
Number of pages9
JournalJournal of Chemical Theory and Computation
Volume15
Issue number3
DOIs
StatePublished - Mar 12 2019

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Rhodopsin
Excitation energy
Density functional theory
Chromophores
density functional theory
proteins
Proteins
chromophores
excitation
perturbation theory
energy
embedding
self consistent fields
methodology
vapor phases
costs
Gases
trends
evaluation
Costs

PubMed: MeSH publication types

  • Journal Article

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Assessment of MC-PDFT Excitation Energies for a Set of QM/MM Models of Rhodopsins. / Marín, María Del Carmen; De Vico, Luca; Dong, Sijia; Gagliardi, Laura; Truhlar, Donald G; Olivucci, Massimo.

In: Journal of Chemical Theory and Computation, Vol. 15, No. 3, 12.03.2019, p. 1915-1923.

Research output: Contribution to journalArticle

Marín, María Del Carmen ; De Vico, Luca ; Dong, Sijia ; Gagliardi, Laura ; Truhlar, Donald G ; Olivucci, Massimo. / Assessment of MC-PDFT Excitation Energies for a Set of QM/MM Models of Rhodopsins. In: Journal of Chemical Theory and Computation. 2019 ; Vol. 15, No. 3. pp. 1915-1923.
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