Redox potentials of aryl derivatives from hybrid functional based first principles molecular dynamics

Xiandong Liu; Jun Cheng; Xiancai Lu; Mengjia He; Rucheng Wang

doi:10.1039/c6cp01375a

Redox potentials of aryl derivatives from hybrid functional based first principles molecular dynamics

Xiandong Liu, Jun Cheng, Xiancai Lu, Mengjia He, Rucheng Wang

Chemistry

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4 Citations (Scopus)

7 Downloads (Pure)

Abstract

We report the redox potentials of a set of organic aryl molecules, including quinones, juglone, tyrosine and tryptophan, calculated using a first principles molecular dynamics (FPMD) based method. The hybrid functional HSE06 reproduces the redox potentials spanning from -0.25 V to 1.15 V within an error of 0.2 V, whereas the errors with the BLYP functional are much larger (up to 0.7 V). It is found that the BLYP functional predicts consistently lower electron affinities/ionization potentials than HSE06 both in gas phase and in an aqueous solution. In water, the ionization potentials are significantly underestimated by BLYP due to the exaggeration of the mixing between the solute states and the valence band states of liquid water. Hybrid HSE06 markedly improves both the solute levels and water band positions, leading to accurate redox potentials. This study suggests that the current FPMD based method at the level of hybrid functionals is able to accurately compute the redox potentials of a wide spectrum of organic molecules.

Original language	English
Pages (from-to)	14911-14917
Number of pages	7
Journal	Physical Chemistry Chemical Physics
Volume	18
Issue number	22
Early online date	4 May 2016
DOIs	https://doi.org/10.1039/c6cp01375a
Publication status	Published - 1 Jun 2016

Bibliographical note

Acknowledgements
We acknowledge the National Science Foundation of China (No.
41222015, 41273074, 41572027 and 21373166), Special Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase), the Foundation for the Author of National Excellent Doctoral Dissertation of P. R. China (No. 201228), Newton International Fellowship Program and the financial support from the State Key Laboratory at Nanjing University. We are grateful to the High Performance Computing Center of Nanjing University for allowing us to use the IBM Blade cluster system.
Open access via RSC Gold for Gold

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Redox potentials of aryl derivatives from hybrid functional based first principles molecular dynamics
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title = "Redox potentials of aryl derivatives from hybrid functional based first principles molecular dynamics",

abstract = "We report the redox potentials of a set of organic aryl molecules, including quinones, juglone, tyrosine and tryptophan, calculated using a first principles molecular dynamics (FPMD) based method. The hybrid functional HSE06 reproduces the redox potentials spanning from -0.25 V to 1.15 V within an error of 0.2 V, whereas the errors with the BLYP functional are much larger (up to 0.7 V). It is found that the BLYP functional predicts consistently lower electron affinities/ionization potentials than HSE06 both in gas phase and in an aqueous solution. In water, the ionization potentials are significantly underestimated by BLYP due to the exaggeration of the mixing between the solute states and the valence band states of liquid water. Hybrid HSE06 markedly improves both the solute levels and water band positions, leading to accurate redox potentials. This study suggests that the current FPMD based method at the level of hybrid functionals is able to accurately compute the redox potentials of a wide spectrum of organic molecules.",

author = "Xiandong Liu and Jun Cheng and Xiancai Lu and Mengjia He and Rucheng Wang",

note = "Acknowledgements We acknowledge the National Science Foundation of China (No. 41222015, 41273074, 41572027 and 21373166), Special Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase), the Foundation for the Author of National Excellent Doctoral Dissertation of P. R. China (No. 201228), Newton International Fellowship Program and the financial support from the State Key Laboratory at Nanjing University. We are grateful to the High Performance Computing Center of Nanjing University for allowing us to use the IBM Blade cluster system. Open access via RSC Gold for Gold",

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AU - Liu, Xiandong

AU - Cheng, Jun

AU - Lu, Xiancai

AU - He, Mengjia

AU - Wang, Rucheng

N1 - Acknowledgements We acknowledge the National Science Foundation of China (No. 41222015, 41273074, 41572027 and 21373166), Special Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase), the Foundation for the Author of National Excellent Doctoral Dissertation of P. R. China (No. 201228), Newton International Fellowship Program and the financial support from the State Key Laboratory at Nanjing University. We are grateful to the High Performance Computing Center of Nanjing University for allowing us to use the IBM Blade cluster system. Open access via RSC Gold for Gold

PY - 2016/6/1

Y1 - 2016/6/1

N2 - We report the redox potentials of a set of organic aryl molecules, including quinones, juglone, tyrosine and tryptophan, calculated using a first principles molecular dynamics (FPMD) based method. The hybrid functional HSE06 reproduces the redox potentials spanning from -0.25 V to 1.15 V within an error of 0.2 V, whereas the errors with the BLYP functional are much larger (up to 0.7 V). It is found that the BLYP functional predicts consistently lower electron affinities/ionization potentials than HSE06 both in gas phase and in an aqueous solution. In water, the ionization potentials are significantly underestimated by BLYP due to the exaggeration of the mixing between the solute states and the valence band states of liquid water. Hybrid HSE06 markedly improves both the solute levels and water band positions, leading to accurate redox potentials. This study suggests that the current FPMD based method at the level of hybrid functionals is able to accurately compute the redox potentials of a wide spectrum of organic molecules.

AB - We report the redox potentials of a set of organic aryl molecules, including quinones, juglone, tyrosine and tryptophan, calculated using a first principles molecular dynamics (FPMD) based method. The hybrid functional HSE06 reproduces the redox potentials spanning from -0.25 V to 1.15 V within an error of 0.2 V, whereas the errors with the BLYP functional are much larger (up to 0.7 V). It is found that the BLYP functional predicts consistently lower electron affinities/ionization potentials than HSE06 both in gas phase and in an aqueous solution. In water, the ionization potentials are significantly underestimated by BLYP due to the exaggeration of the mixing between the solute states and the valence band states of liquid water. Hybrid HSE06 markedly improves both the solute levels and water band positions, leading to accurate redox potentials. This study suggests that the current FPMD based method at the level of hybrid functionals is able to accurately compute the redox potentials of a wide spectrum of organic molecules.

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SP - 14911

EP - 14917

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

IS - 22

ER -

Redox potentials of aryl derivatives from hybrid functional based first principles molecular dynamics

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