Polarizable Embedding for Excited-State Reactions: Dynamically Weighted Polarizable QM/MM

Muhammad A Hagras; William J Glover

doi:10.1021/acs.jctc.8b00064

Polarizable Embedding for Excited-State Reactions: Dynamically Weighted Polarizable QM/MM

J Chem Theory Comput. 2018 Apr 10;14(4):2137-2144. doi: 10.1021/acs.jctc.8b00064. Epub 2018 Mar 28.

Authors

Muhammad A Hagras^{1

2}, William J Glover^{3

4

2

5}

Affiliations

¹ NYU Shanghai , 14 East Fourth Street , New York , New York 10003 , United States.
² Department of Chemistry , New York University , New York , New York 10003 , United States.
³ NYU Shanghai , 1555 Century Avenue , Shanghai 200122 , China.
⁴ NYU-ECNU Center for Computational Chemistry at NYU Shanghai , 3663 Zhongshan Road North , Shanghai 200062 , China.
⁵ Department of Chemistry , East China Normal University , Shanghai 200062 , China.

PMID: 29561617
DOI: 10.1021/acs.jctc.8b00064

Abstract

Recent interest in polarizable embedding methods for electronic excited states has so far been focused on optical absorption and emission spectra calculations. To explore the suitability of these methods for excited-state reactions, we constructed a simple molecular system with an electronic crossing coupled to a polarizable species: the triatomic LiFBe. We found that current polarizable QM/MM methods inadequately describe the potential energy surfaces in this system, particularly close to the electronic crossing, so we developed a new polarizable embedding method called dynamically weighted polarizable QM/MM. The new method reproduces the potential energy surfaces of LiFBe from full-system multireference configuration interaction singles and doubles calculations with near-quantitative accuracy.