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Multireference exciplex binding energies: Basis set convergence and error

Krueger, Rachel A. and Blanquart, Guillaume (2019) Multireference exciplex binding energies: Basis set convergence and error. International Journal of Quantum Chemistry, 119 (5). Art. No. e25819. ISSN 0020-7608.

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In multichromophore systems, characterization of electronic structure requires characterization of exciplexes, electron‐hole pairs delocalized over multiple molecules. Computing exciplex binding energy requires an accurate description of both the noncovalent interactions between the chromophores and their excited electronic states. The critical role of basis set selection for accurate description of noncovalent interactions is well known, but for some of the most accurate excited‐state methods, basis set dependence is incompletely understood. In this work, the impact of basis set size and diffuseness on CASSCF/NEVPT2 binding energies is determined for three systems in their lowest singlet excited states: the benzene excimer, the cis‐butadiene‐benzene exciplex, and the benzene‐naphthalene exciplex. We demonstrate that excellent CBS binding energies may be obtained using the moderately‐sized jun‐cc‐pV(D + d)Z and jun‐cc‐pV(T + d)Z basis sets and a simple N^(−3) model. Repeating this procedure with the N = 3, 4 basis sets from the most diffuse basis set family applied to each system yields a binding energy of 56.6 ± 1.2 kJ/mol for the benzene excimer and binding energies of 11.1 ± 0.5 kJ/mol and 19.2 ± 1.7 kJ/mol for the cis‐butadiene‐benzene exciplex and the benzene‐naphthalene exciplex, respectively.

Item Type:Article
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URLURL TypeDescription
Krueger, Rachel A.0000-0002-5457-2931
Blanquart, Guillaume0000-0002-5074-9728
Additional Information:© 2018 Wiley Periodicals, Inc. Version of Record online: 14 October 2018; Manuscript accepted: 11 September 2018; Manuscript received: 20 July 2018. Funding: Division of Graduate Education, National Science Foundation. Grant Number: DGE‐1745301.
Funding AgencyGrant Number
NSF Graduate Research FellowshipDGE-1745301
Subject Keywords:basis set error; exciplex formation; molecular photophysics; multireference methods
Record Number:CaltechAUTHORS:20181105-081552037
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Official Citation:Krueger RA, Blanquart G. Multireference exciplex binding energies: Basis set convergence and error. Int J Quantum Chem. 2019;119:e25819.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:90625
Deposited By: Tony Diaz
Deposited On:06 Nov 2018 18:23
Last Modified:17 Jan 2019 22:44

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