TY - JOUR
T1 - Evidence of Skewness and Sub-Gaussian Character in Temperature-Dependent Distributions of One Million Electronic Excitation Energies in PbS Quantum Dots
AU - Scher, Jeremy A.
AU - Govind, Niranjan
AU - Chakraborty, Arindam
N1 - Publisher Copyright:
Copyright © 2020 American Chemical Society.
PY - 2020/2/6
Y1 - 2020/2/6
N2 - 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.
AB - 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.
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U2 - 10.1021/acs.jpclett.9b03103
DO - 10.1021/acs.jpclett.9b03103
M3 - Article
C2 - 31927924
AN - SCOPUS:85079075408
SN - 1948-7185
VL - 11
SP - 986
EP - 992
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 3
ER -