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Title: Spectral Signatures of Ultrafast Excited-State Intramolecular Proton Transfer from Computational Multi-edge Transient X-ray Absorption Spectroscopy

Abstract

Excited state intramolecular proton transfer (ESIPT) is a fundamental chemical process with several applications. Ultrafast ESIPT involves coupled electronic and atomic motions and has been primarily studied using femtosecond optical spectroscopy. X-ray spectroscopy is particularly useful because it is element-specic and enables direct, individual probes of the proton donating and accepting atoms. Here, we report a computational study to resolve the ESIPT in 10-Hydroxybenzo[h]quinoline (HBQ), an intramolecularly hydrogen bonded compound, using time-dependent density functional theory combined with ab initio molecular dynamics (AIMD) and time-resolved X-ray absorption spectroscopy (XAS) computations to track the ultrafast excited-state dynamics. Overall, our results reveal clear X-ray spectral signatures of coupled electronic and atomic motions during and following ESIPT at the oxygen and nitrogen K-edge paving the way for future experiments at X-ray free electron lasers.

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Washington, Seattle, WA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1829715
Report Number(s):
PNNL-SA-164927
Journal ID: ISSN 1948-7185
Grant/Contract Number:  
AC05-76RL01830; CHE-1856413; KC-030105172685
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 12; Journal Issue: 40; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; X-rays; Oxygen; Nitrogen; Molecular orbitals; Mathematical methods

Citation Formats

Loe, Caroline M., Liekhus-Schmaltz, Chelsea, Govind, Niranjan, and Khalil, Munira. Spectral Signatures of Ultrafast Excited-State Intramolecular Proton Transfer from Computational Multi-edge Transient X-ray Absorption Spectroscopy. United States: N. p., 2021. Web. doi:10.1021/acs.jpclett.1c02483.
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Loe, Caroline M., Liekhus-Schmaltz, Chelsea, Govind, Niranjan, & Khalil, Munira. Spectral Signatures of Ultrafast Excited-State Intramolecular Proton Transfer from Computational Multi-edge Transient X-ray Absorption Spectroscopy. United States. https://doi.org/10.1021/acs.jpclett.1c02483
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Loe, Caroline M., Liekhus-Schmaltz, Chelsea, Govind, Niranjan, and Khalil, Munira. Mon . "Spectral Signatures of Ultrafast Excited-State Intramolecular Proton Transfer from Computational Multi-edge Transient X-ray Absorption Spectroscopy". United States. https://doi.org/10.1021/acs.jpclett.1c02483. https://www.osti.gov/servlets/purl/1829715.
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@article{osti_1829715,
title = {Spectral Signatures of Ultrafast Excited-State Intramolecular Proton Transfer from Computational Multi-edge Transient X-ray Absorption Spectroscopy},
author = {Loe, Caroline M. and Liekhus-Schmaltz, Chelsea and Govind, Niranjan and Khalil, Munira},
abstractNote = {Excited state intramolecular proton transfer (ESIPT) is a fundamental chemical process with several applications. Ultrafast ESIPT involves coupled electronic and atomic motions and has been primarily studied using femtosecond optical spectroscopy. X-ray spectroscopy is particularly useful because it is element-specic and enables direct, individual probes of the proton donating and accepting atoms. Here, we report a computational study to resolve the ESIPT in 10-Hydroxybenzo[h]quinoline (HBQ), an intramolecularly hydrogen bonded compound, using time-dependent density functional theory combined with ab initio molecular dynamics (AIMD) and time-resolved X-ray absorption spectroscopy (XAS) computations to track the ultrafast excited-state dynamics. Overall, our results reveal clear X-ray spectral signatures of coupled electronic and atomic motions during and following ESIPT at the oxygen and nitrogen K-edge paving the way for future experiments at X-ray free electron lasers.},
doi = {10.1021/acs.jpclett.1c02483},
journal = {Journal of Physical Chemistry Letters},
number = 40,
volume = 12,
place = {United States},
year = {Mon Oct 04 00:00:00 EDT 2021},
month = {Mon Oct 04 00:00:00 EDT 2021}
}
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https://doi.org/10.1021/acs.jpclett.1c02483
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Works referenced in this record:

The role of databases in support of computational chemistry calculations
journal, October 1996

Probing ultrafast vibrational dynamics of intramolecular hydrogen bonds with broadband infrared pump-probe spectroscopy
journal, March 2019

Advanced Organic Optoelectronic Materials: Harnessing Excited-State Intramolecular Proton Transfer (ESIPT) Process
journal, July 2011

NWChem: Past, present, and future
journal, May 2020

  • Aprà, E.; Bylaska, E. J.; de Jong, W. A.
  • The Journal of Chemical Physics, Vol. 152, Issue 18
  • DOI: 10.1063/5.0004997

Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988

Linear-Response and Real-Time Time-Dependent Density Functional Theory Studies of Core-Level Near-Edge X-Ray Absorption
journal, August 2012

  • Lopata, K.; Van Kuiken, B. E.; Khalil, M.
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 9
  • DOI: 10.1021/ct3005613

Excited-state intramolecular proton-transfer (ESIPT) based fluorescence sensors and imaging agents
journal, January 2018

  • Sedgwick, Adam C.; Wu, Luling; Han, Hai-Hao
  • Chemical Society Reviews, Vol. 47, Issue 23
  • DOI: 10.1039/C8CS00185E

Dynamics of excited state proton transfer in nitro substituted 10-hydroxybenzo[h]quinolines
journal, January 2017

  • Marciniak, H.; Hristova, S.; Deneva, V.
  • Phys. Chem. Chem. Phys., Vol. 19, Issue 39
  • DOI: 10.1039/C7CP04476C

Basis Set Exchange:  A Community Database for Computational Sciences
journal, March 2007

  • Schuchardt, Karen L.; Didier, Brett T.; Elsethagen, Todd
  • Journal of Chemical Information and Modeling, Vol. 47, Issue 3
  • DOI: 10.1021/ci600510j

COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient
journal, January 1993

Simulating One-Photon Absorption and Resonance Raman Scattering Spectra Using Analytical Excited State Energy Gradients within Time-Dependent Density Functional Theory
journal, November 2013

  • Silverstein, Daniel W.; Govind, Niranjan; van Dam, Hubertus J. J.
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 12
  • DOI: 10.1021/ct4007772

10-Hydroxybenzo[h]quinoline: switching between single- and double-well proton transfer through structural modifications
journal, January 2015

  • Hristova, S.; Dobrikov, G.; Kamounah, F. S.
  • RSC Advances, Vol. 5, Issue 124
  • DOI: 10.1039/C5RA20057A

A White-Light-Emitting Molecule: Frustrated Energy Transfer between Constituent Emitting Centers
journal, October 2009

  • Park, Sanghyuk; Kwon, Ji Eon; Kim, Se Hun
  • Journal of the American Chemical Society, Vol. 131, Issue 39
  • DOI: 10.1021/ja902533f

Correlating Infrared and X-ray Absorption Energies for Molecular-Level Insight into Hydrogen Bond Making and Breaking in Solution
journal, June 2015

  • Prémont-Schwarz, Mirabelle; Schreck, Simon; Iannuzzi, Marcella
  • The Journal of Physical Chemistry B, Vol. 119, Issue 25
  • DOI: 10.1021/acs.jpcb.5b02954

Coherent excited state intramolecular proton transfer probed by time-resolved fluorescence
journal, January 2009

  • Kim, Chul Hoon; Joo, Taiha
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 44
  • DOI: 10.1039/b915768a

New Basis Set Exchange: An Open, Up-to-Date Resource for the Molecular Sciences Community
journal, October 2019

  • Pritchard, Benjamin P.; Altarawy, Doaa; Didier, Brett
  • Journal of Chemical Information and Modeling, Vol. 59, Issue 11
  • DOI: 10.1021/acs.jcim.9b00725

Ultrafast Independent N−H and N−C Bond Deformation Investigated with Resonant Inelastic X-Ray Scattering
journal, April 2017

  • Eckert, Sebastian; Norell, Jesper; Miedema, Piter S.
  • Angewandte Chemie International Edition, Vol. 56, Issue 22
  • DOI: 10.1002/anie.201700239

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010

  • Valiev, M.; Bylaska, E. J.; Govind, N.
  • Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
  • DOI: 10.1016/j.cpc.2010.04.018

Near-Edge X-ray Absorption Fine Structure Spectroscopy of Heteroatomic Core-Hole States as a Probe for Nearly Indistinguishable Chemical Environments
journal, December 2019

  • Nascimento, Daniel R.; Zhang, Yu; Bergmann, Uwe
  • The Journal of Physical Chemistry Letters, Vol. 11, Issue 2
  • DOI: 10.1021/acs.jpclett.9b03500

Excited-State Intramolecular Proton Transfer in 10-Hydroxybenzo[h]quinoline
journal, February 2001

  • Chou, Pi-Tai; Chen, Youn-Chan; Yu, Wei-Shan
  • The Journal of Physical Chemistry A, Vol. 105, Issue 10
  • DOI: 10.1021/jp002942w

Infrared and Raman Spectroscopy from Ab Initio Molecular Dynamics and Static Normal Mode Analysis: The C–H Region of DMSO as a Case Study
journal, August 2015

  • Fischer, Sean A.; Ueltschi, Tyler W.; El-Khoury, Patrick Z.
  • The Journal of Physical Chemistry B, Vol. 120, Issue 8
  • DOI: 10.1021/acs.jpcb.5b03323

Soft X-ray Spectroscopy of the Amine Group: Hydrogen Bond Motifs in Alkylamine/Alkylammonium Acid–Base Pairs
journal, July 2018

  • Ekimova, Maria; Kubin, Markus; Ochmann, Miguel
  • The Journal of Physical Chemistry B, Vol. 122, Issue 31
  • DOI: 10.1021/acs.jpcb.8b05424

Molecular structures and protonation state of 2-Mercaptopyridine in aqueous solution
journal, March 2016

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a

Ab initio simulations of complementary K-edges and solvatization effects for detection of proton transfer in aqueous 2-thiopyridone
journal, September 2019

  • Norell, J.; Eckert, S.; Van Kuiken, B. E.
  • The Journal of Chemical Physics, Vol. 151, Issue 11
  • DOI: 10.1063/1.5109840

Photochromic Switching of Excited-State Intramolecular Proton-Transfer (ESIPT) Fluorescence:  A Unique Route to High-Contrast Memory Switching and Nondestructive Readout
journal, October 2006

  • Lim, Seon-Jeong; Seo, Jangwon; Park, Soo Young
  • Journal of the American Chemical Society, Vol. 128, Issue 45
  • DOI: 10.1021/ja0637604

Resonant Stimulated X-ray Raman Spectroscopy of Mixed-Valence Manganese Complexes
journal, June 2021

  • Cavaletto, Stefano M.; Nascimento, Daniel R.; Zhang, Yu
  • The Journal of Physical Chemistry Letters, Vol. 12, Issue 25
  • DOI: 10.1021/acs.jpclett.1c01190

A novel excited-state intramolecular proton transfer molecule, 10-hydroxybenzo[h]quinoline
journal, May 1992

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988

Active Role of Proton in Excited State Intramolecular Proton Transfer Reaction
journal, February 2013

  • Lee, Junghwa; Kim, Chul Hoon; Joo, Taiha
  • The Journal of Physical Chemistry A, Vol. 117, Issue 7
  • DOI: 10.1021/jp311884b

Aqueous Solvation of Ammonia and Ammonium: Probing Hydrogen Bond Motifs with FT-IR and Soft X-ray Spectroscopy
journal, August 2017

  • Ekimova, Maria; Quevedo, Wilson; Szyc, Łukasz
  • Journal of the American Chemical Society, Vol. 139, Issue 36
  • DOI: 10.1021/jacs.7b07207

Nuclear quantum effects enter the mainstream
journal, February 2018

Direct Simulation of Excited-State Intramolecular Proton Transfer and Vibrational Coherence of 10-Hydroxybenzo[h]quinoline in Solution
journal, August 2011

  • Higashi, Masahiro; Saito, Shinji
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 18
  • DOI: 10.1021/jz201042u

Theoretical study on influence of geometry controlling over the excited-state intramolecular proton transfer of 10-hydroxybenzo[ h ]quinoline and its derivatives
journal, August 2017

  • Chansen, Warinthon; Salaeh, Rusrina; Prommin, Chanatkran
  • Computational and Theoretical Chemistry, Vol. 1113
  • DOI: 10.1016/j.comptc.2017.05.008

Observation of the fastest chemical processes in the radiolysis of water
journal, January 2020

A Smooth Solvation Potential Based on the Conductor-Like Screening Model
journal, December 1999

  • York, Darrin M.; Karplus, Martin
  • The Journal of Physical Chemistry A, Vol. 103, Issue 50
  • DOI: 10.1021/jp992097l

A Highly Selective Pyrophosphate Sensor Based on ESIPT Turn-On in Water
journal, March 2011

  • Chen, Wei-Hua; Xing, Yu; Pang, Yi
  • Organic Letters, Vol. 13, Issue 6
  • DOI: 10.1021/ol200054w

Multidimensional Attosecond Resonant X-Ray Spectroscopy of Molecules: Lessons from the Optical Regime
journal, April 2013

Non-Born–Oppenheimer Molecular Dynamics Observed by Coherent Nuclear Wave Packets
journal, January 2020

  • Kim, JunWoo; Kim, Chul Hoon; Burger, Christian
  • The Journal of Physical Chemistry Letters, Vol. 11, Issue 3
  • DOI: 10.1021/acs.jpclett.9b03488

Entangled Valence Electron–Hole Dynamics Revealed by Stimulated Attosecond X-ray Raman Scattering
journal, August 2012

  • Healion, Daniel; Zhang, Yu; Biggs, Jason D.
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 17
  • DOI: 10.1021/jz300981w
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