Evidence of Skewness and Sub-Gaussian Character in Temperature-Dependent Distributions of One Million Electronic Excitation Energies in PbS Quantum Dots

Jeremy A. Scher, Niranjan Govind, Arindam Chakraborty

Research output: Contribution to journalArticle

Abstract

Obtaining statistical distributions by sampling a large number of conformations is vital for an accurate description of temperature-dependent properties of chemical systems. However, constructing distributions with 105-106 samples is computationally challenging because of the prohibitively high computational cost of performing first-principles quantum mechanical calculations. In this work, we present a new technique called the effective stochastic potential configuration interaction singles (ESP-CIS) method to obtain excitation energies. The ESP-CIS method uses random matrix theory for the construction of an effective stochastic representation of the Fock operator and combines it with the CIS method. Excited-state energies of PbS quantum dots (0.75-1.75 nm) at temperatures of 10-400 K were calculated using the ESP-CIS method. Results from a total of 27 million excitation energy calculations revealed the distributions to be sub-Gaussian in nature with negative skewness, which progressively became red-shifted with increasing temperature. This study demonstrates the efficacy of the ESP-CIS method as a general-purpose method for efficient excited-state calculations.

Original languageEnglish (US)
Pages (from-to)986-992
Number of pages7
JournalThe journal of physical chemistry letters
Volume11
Issue number3
DOIs
StatePublished - Feb 6 2020

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

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