Nitrile Vibration Reports Induced Electric Field and Delocalization of Electron in the Charge-Transfer State of Aryl Nitriles

Mani, Tomoyasu; Grills, David C.

doi:10.1021/acs.jpca.8b08025

Nitrile Vibration Reports Induced Electric Field and Delocalization of Electron in the Charge-Transfer State of Aryl Nitriles

Journal Article · Fri Aug 24 00:00:00 UTC 2018 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.8b08025· OSTI ID:1473657

^[1]; ^[2]

Univ. of Connecticut, Storrs, CT (United States). Department of Chemistry
Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division

An electric field is created upon photoinduced charge separation in electron donor–acceptor (D–A) molecules. The photophysics of a prototypical D–A molecule, 4-(dimethylamino)-benzonitrile (DMABN), has been under extensive investigation for decades. Here in this paper, by using the framework of the vibrational Stark effect (VSE), we show that the nitrile vibration quantifies a significant induced electric field in the intramolecular charge-transfer state of DMABN. We further demonstrate that such a phenomenon can be observed in a structurally similar aryl nitrile and that the VSE depends on solvent polarity due to dielectric screening. Finally, our current work shows how the superb sensitivity of the nitrile vibration can be used to identify the nature of electron delocalization and quantify the induced electric field in photoinduced charge transfer processes.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0012704

OSTI ID:: 1473657

Report Number(s):: BNL--209069-2018-JAAM

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 37 Vol. 122; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (56)

Umwandlung von Elektronenanregungsenergie Lippert, E.; Lüder, W.; Moll, F. Angewandte Chemie, Vol. 73, Issue 21 https://doi.org/10.1002/ange.19610732103	journal	November 1961
Charge Separation in Excited States of Decoupled Systems?TICT Compounds and Implications Regarding the Development of New Laser Dyes and the Primary Process of Vision and Photosynthesis Rettig, Wolfgang Angewandte Chemie International Edition in English, Vol. 25, Issue 11 https://doi.org/10.1002/anie.198609711	journal	November 1986
Direct Observation of a Hydrogen-Bonded Charge-Transfer State of 4-Dimethylaminobenzonitrile in Methanol by Time-Resolved IR Spectroscopy Kwok, Wai-Ming; George, Michael W.; Grills, David C. Angewandte Chemie International Edition, Vol. 42, Issue 16 https://doi.org/10.1002/anie.200219816	journal	April 2003
Reinterpretation of the anomalous fluorescense of p-n,n-dimethylamino-benzonitrile Rotkiewicz, K.; Grellmann, K. H.; Grabowski, Z. R. Chemical Physics Letters, Vol. 19, Issue 3 https://doi.org/10.1016/0009-2614(73)80367-7	journal	April 1973
Thermochromic shifts of the fluorescence spectra of 4-N,N-dimethylaminobenzonitrile in solution Suppan, Paul Journal of Luminescence, Vol. 33, Issue 1 https://doi.org/10.1016/0022-2313(85)90026-2	journal	March 1985
Relation between the electronic structure and infrared frequencies of the cyano-group in alkali-metal complexes of some substituted benzonitriles Juchnovski, I. N.; Binev, I. G. Journal of Molecular Structure, Vol. 7, Issue 3-4 https://doi.org/10.1016/0022-2860(71)87021-7	journal	February 1971
Considerations on the dipole moment of molecules forming the twisted intramolecular charge transfer state Baumann, Wolfram; Bischof, H.; Fröhling, J. -C. Journal of Photochemistry and Photobiology A: Chemistry, Vol. 64, Issue 1 https://doi.org/10.1016/1010-6030(92)85093-A	journal	March 1992
Time-resolved resonance Raman spectra of the intramolecular charge transfer state of DMABN Kwok, W. M.; Ma, C.; Matousek, P. Chemical Physics Letters, Vol. 322, Issue 5 https://doi.org/10.1016/S0009-2614(00)00436-X	journal	May 2000
Resonance Raman study of ring deuterated 4-dimethylaminobenzonitrile (DMABN-d4): the ground, ICT and triplet states Ma, C.; Kwok, W. M.; Matousek, P. Journal of Photochemistry and Photobiology A: Chemistry, Vol. 142, Issue 2-3 https://doi.org/10.1016/S1010-6030(01)00512-3	journal	September 2001
Looking at Photoinduced Charge Transfer Processes in the IR: Answers to Several Long-Standing Questions Dereka, Bogdan; Koch, Marius; Vauthey, Eric Accounts of Chemical Research, Vol. 50, Issue 2 https://doi.org/10.1021/acs.accounts.6b00538	journal	January 2017
Identification of Ion-Pair Structures in Solution by Vibrational Stark Effects Hack, John; Grills, David C.; Miller, John R. The Journal of Physical Chemistry B, Vol. 120, Issue 6 https://doi.org/10.1021/acs.jpcb.5b11893	journal	February 2016
Probing Intermolecular Electron Delocalization in Dimer Radical Anions by Vibrational Spectroscopy Mani, Tomoyasu; Grills, David C. The Journal of Physical Chemistry B, Vol. 121, Issue 30 https://doi.org/10.1021/acs.jpcb.7b02559	journal	July 2017
Ultrafast Raman Spectroscopy as a Probe of Local Structure and Dynamics in Photoexcited Conjugated Materials Bragg, Arthur E.; Yu, Wenjian; Zhou, Jiawang The Journal of Physical Chemistry Letters, Vol. 7, Issue 19 https://doi.org/10.1021/acs.jpclett.6b01060	journal	September 2016
Impact of Local Electric Fields on Charge-Transfer Processes at the TiO ₂ /Dye/Electrolyte Interface Yang, Wenxing; Vlachopoulos, Nick; Boschloo, Gerrit ACS Energy Letters, Vol. 2, Issue 1 https://doi.org/10.1021/acsenergylett.6b00568	journal	December 2016
Electron-Transfer Acceleration Investigated by Time Resolved Infrared Spectroscopy Vlček, Antonín; Kvapilová, Hana; Towrie, Michael Accounts of Chemical Research, Vol. 48, Issue 3 https://doi.org/10.1021/ar5004048	journal	February 2015
Measuring Electric Fields and Noncovalent Interactions Using the Vibrational Stark Effect Fried, Stephen D.; Boxer, Steven G. Accounts of Chemical Research, Vol. 48, Issue 4 https://doi.org/10.1021/ar500464j	journal	March 2015
Role of the πσ* State in Molecular Photophysics Zgierski, Marek Z.; Fujiwara, Takashige; Lim, Edward C. Accounts of Chemical Research, Vol. 43, Issue 4 https://doi.org/10.1021/ar9002043	journal	January 2010
Structural Changes Accompanying Intramolecular Electron Transfer: Focus on Twisted Intramolecular Charge-Transfer States and Structures Grabowski, Zbigniew R.; Rotkiewicz, Krystyna; Rettig, Wolfgang Chemical Reviews, Vol. 103, Issue 10 https://doi.org/10.1021/cr940745l	journal	October 2003
Quantum Mechanical Continuum Solvation Models Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto Chemical Reviews, Vol. 105, Issue 8 https://doi.org/10.1021/cr9904009	journal	August 2005
Structure of the Twisted-Intramolecular-Charge-Transfer Excited Singlet and Triplet States of 4-(Dimethylamino)benzonitrile As Studied by Nanosecond Time-Resolved Infrared Spectroscopy Hashimoto, Mamoru; Hamaguchi, Hiro-o The Journal of Physical Chemistry, Vol. 99, Issue 20 https://doi.org/10.1021/j100020a008	journal	May 1995
Molecular conformation and excited-state dipole moments of di- and tetramethylaminobenzonitrile (DMABN and TMABN) Rettig, Wolfgang; Braun, David; Suppan, Paul The Journal of Physical Chemistry, Vol. 97, Issue 51 https://doi.org/10.1021/j100153a014	journal	December 1993
Excited-state dipole moments of dual fluorescent 4-(dialkylamino)benzonitriles: influence of alkyl chain length and effective solvent polarity Schuddeboom, Wouter; Jonker, Stephan A.; Warman, John M. The Journal of Physical Chemistry, Vol. 96, Issue 26 https://doi.org/10.1021/j100205a041	journal	December 1992
Photoinduced Intramolecular Charge Transfer in 4-(Dimethyl)aminobenzonitrile − A Theoretical Perspective Rappoport, Dmitrij; Furche, Filipp Journal of the American Chemical Society, Vol. 126, Issue 4 https://doi.org/10.1021/ja037806u	journal	February 2004
Ultrafast Vibrational Stark-Effect Spectroscopy: Exploring Charge-Transfer Reactions by Directly Monitoring the Solvation Shell Response Baiz, Carlos R.; Kubarych, Kevin J. Journal of the American Chemical Society, Vol. 132, Issue 37 https://doi.org/10.1021/ja1043853	journal	September 2010
Polarons, Bipolarons, and Side-By-Side Polarons in Reduction of Oligofluorenes Zaikowski, Lori; Kaur, Parmeet; Gelfond, Claudia Journal of the American Chemical Society, Vol. 134, Issue 26 https://doi.org/10.1021/ja301494n	journal	June 2012
Vibrational Stark Effects To Identify Ion Pairing and Determine Reduction Potentials in Electrolyte-Free Environments Mani, Tomoyasu; Grills, David C.; Miller, John R. Journal of the American Chemical Society, Vol. 137, Issue 3 https://doi.org/10.1021/ja512302c	journal	January 2015
Stark Effects after Excited-State Interfacial Electron Transfer at Sensitized TiO ₂ Nanocrystallites Ardo, Shane; Sun, Yali; Staniszewski, Aaron Journal of the American Chemical Society, Vol. 132, Issue 19 https://doi.org/10.1021/ja909781g	journal	May 2010
Shedding Light on Excited-State Structures by Theoretical Analysis of Femtosecond Transient Infrared Spectra: Intramolecular Charge Transfer in 4-(Dimethylamino)benzonitrile Dreyer, Jens; Kummrow, Andreas Journal of the American Chemical Society, Vol. 122, Issue 11 https://doi.org/10.1021/ja992095e	journal	March 2000
Electron Localization of Anions Probed by Nitrile Vibrations Mani, Tomoyasu; Grills, David C.; Newton, Marshall D. Journal of the American Chemical Society, Vol. 137, Issue 34 https://doi.org/10.1021/jacs.5b04648	journal	August 2015
Charge Localization after Ultrafast Photoexcitation of a Rigid Perylene Perylenediimide Dyad Visualized by Transient Stark Effect Koch, Marius; Myahkostupov, Mykhaylo; Oblinsky, Daniel G. Journal of the American Chemical Society, Vol. 139, Issue 15 https://doi.org/10.1021/jacs.7b01630	journal	April 2017
A Determination of the Structure of the Intramolecular Charge Transfer State of 4-Dimethylaminobenzonitrile (DMABN) by Time-Resolved Resonance Raman Spectroscopy Kwok, W. M.; Ma, C.; Matousek, P. The Journal of Physical Chemistry A, Vol. 105, Issue 6 https://doi.org/10.1021/jp003705w	journal	January 2001
Picosecond Infrared Spectra of Isotope-Substituted 4-(Dimethylamino)benzonitriles and Molecular Structure of the Charge-Transfer Singlet Excited State Okamoto, Hiromi; Inishi, Hironori; Nakamura, Yuko The Journal of Physical Chemistry A, Vol. 105, Issue 17 https://doi.org/10.1021/jp0039363	journal	April 2001
Time-Resolved Study of the Triplet State of 4-dimethylaminobenzonitrile (DMABN) Ma, C.; Kwok, W. M.; Matousek, P. The Journal of Physical Chemistry A, Vol. 105, Issue 19 https://doi.org/10.1021/jp004497a	journal	May 2001
Probing the Charge Transfer Reaction Coordinate of 4-(Dimethylamino)benzonitrile with Femtosecond Stimulated Raman Spectroscopy ^† Rhinehart, Justin M.; Mehlenbacher, Randy D.; McCamant, David The Journal of Physical Chemistry B, Vol. 114, Issue 45 https://doi.org/10.1021/jp1023982	journal	November 2010
Solvent-Induced Infrared Frequency Shifts in Aromatic Nitriles Are Quantitatively Described by the Vibrational Stark Effect Levinson, Nicholas M.; Fried, Stephen D.; Boxer, Steven G. The Journal of Physical Chemistry B, Vol. 116, Issue 35 https://doi.org/10.1021/jp301054e	journal	April 2012
Multimode Charge-Transfer Dynamics of 4-(Dimethylamino)benzonitrile Probed with Ultraviolet Femtosecond Stimulated Raman Spectroscopy Rhinehart, Justin M.; Challa, J. Reddy; McCamant, David W. The Journal of Physical Chemistry B, Vol. 116, Issue 35 https://doi.org/10.1021/jp3020645	journal	May 2012
Stark Realities ^† Boxer, Steven G. The Journal of Physical Chemistry B, Vol. 113, Issue 10 https://doi.org/10.1021/jp8067393	journal	March 2009
Direct Measurement of the Membrane Dipole Field in Bicelles Using Vibrational Stark Effect Spectroscopy Hu, Wenhui; Webb, Lauren J. The Journal of Physical Chemistry Letters, Vol. 2, Issue 15 https://doi.org/10.1021/jz200729a	journal	July 2011
Imaging Electric Fields in SERS and TERS Using the Vibrational Stark Effect Marr, James M.; Schultz, Zachary D. The Journal of Physical Chemistry Letters, Vol. 4, Issue 19 https://doi.org/10.1021/jz401551u	journal	September 2013
Electrostatic catalysis of a Diels–Alder reaction Aragonès, Albert C.; Haworth, Naomi L.; Darwish, Nadim Nature, Vol. 531, Issue 7592 https://doi.org/10.1038/nature16989	journal	March 2016
Vibrational solvatochromism of nitrile infrared probes: beyond the vibrational Stark dipole approach Błasiak, Bartosz; Ritchie, Andrew W.; Webb, Lauren J. Physical Chemistry Chemical Physics, Vol. 18, Issue 27 https://doi.org/10.1039/C6CP01578F	journal	January 2016
Detection of electron tunneling across plasmonic nanoparticle–film junctions using nitrile vibrations Wang, Hao; Yao, Kun; Parkhill, John A. Physical Chemistry Chemical Physics, Vol. 19, Issue 8 https://doi.org/10.1039/C6CP08168A	journal	January 2017
Further time-resolved spectroscopic investigations on the intramolecular charge transfer state of 4-dimethylaminobenzonitrile (DMABN) and its derivatives, 4-diethylaminobenzonitrile (DEABN) and 4-dimethylamino-3,5-dimethylbenzonitrile (TMABN)Dedicated to Professor Dr Z. R. Grabowski and Professor Dr J. Wirz on the occasions of their 75th and 60th birthdays. Kwok, W. M.; Ma, C.; George, M. W. Physical Chemistry Chemical Physics, Vol. 5, Issue 6 https://doi.org/10.1039/b209621h	journal	January 2003
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections Chai, Jeng-Da; Head-Gordon, Martin Physical Chemistry Chemical Physics, Vol. 10, Issue 44 https://doi.org/10.1039/b810189b	journal	January 2008
A quantitative theory and computational approach for the vibrational Stark effect Brewer, Scott H.; Franzen, Stefan The Journal of Chemical Physics, Vol. 119, Issue 2 https://doi.org/10.1063/1.1578471	journal	July 2003
The LEAF picosecond pulse radiolysis facility at Brookhaven National Laboratory Wishart, James F.; Cook, Andrew R.; Miller, John R. Review of Scientific Instruments, Vol. 75, Issue 11 https://doi.org/10.1063/1.1807004	journal	November 2004
A state-specific polarizable continuum model time dependent density functional theory method for excited state calculations in solution Improta, Roberto; Barone, Vincenzo; Scalmani, Giovanni The Journal of Chemical Physics, Vol. 125, Issue 5 https://doi.org/10.1063/1.2222364	journal	August 2006
Importance of short-range versus long-range Hartree-Fock exchange for the performance of hybrid density functionals Vydrov, Oleg A.; Heyd, Jochen; Krukau, Aliaksandr V. The Journal of Chemical Physics, Vol. 125, Issue 7 https://doi.org/10.1063/1.2244560	journal	August 2006
Assessment of a long-range corrected hybrid functional Vydrov, Oleg A.; Scuseria, Gustavo E. The Journal of Chemical Physics, Vol. 125, Issue 23 https://doi.org/10.1063/1.2409292	journal	December 2006
Tests of functionals for systems with fractional electron number Vydrov, Oleg A.; Scuseria, Gustavo E.; Perdew, John P. The Journal of Chemical Physics, Vol. 126, Issue 15 https://doi.org/10.1063/1.2723119	journal	April 2007
Toward effective and reliable fluorescence energies in solution by a new state specific polarizable continuum model time dependent density functional theory approach Improta, Roberto; Scalmani, Giovanni; Frisch, Michael J. The Journal of Chemical Physics, Vol. 127, Issue 7 https://doi.org/10.1063/1.2757168	journal	August 2007
Vibrational phase and energy relaxation of CN− in water Rey, Rossend; Hynes, James T. The Journal of Chemical Physics, Vol. 108, Issue 1 https://doi.org/10.1063/1.475389	journal	January 1998
Development of nanosecond time-resolved infrared detection at the LEAF pulse radiolysis facility Grills, David C.; Farrington, Jaime A.; Layne, Bobby H. Review of Scientific Instruments, Vol. 86, Issue 4 https://doi.org/10.1063/1.4918728	journal	April 2015
Extreme electric fields power catalysis in the active site of ketosteroid isomerase Fried, Stephen D.; Bagchi, Sayan; Boxer, Steven G. Science, Vol. 346, Issue 6216 https://doi.org/10.1126/science.1259802	journal	December 2014
STARK SPECTROSCOPY: Applications in Chemistry, Biology, and Materials Science Bublitz, Gerold U.; Boxer, Steven G. Annual Review of Physical Chemistry, Vol. 48, Issue 1 https://doi.org/10.1146/annurev.physchem.48.1.213	journal	October 1997
Application of External-Cavity Quantum Cascade Infrared Lasers to Nanosecond Time-Resolved Infrared Spectroscopy of Condensed-Phase Samples following Pulse Radiolysis Grills, David C.; Cook, Andrew R.; Fujita, Etsuko Applied Spectroscopy, Vol. 64, Issue 6 https://doi.org/10.1366/000370210791414344	journal	June 2010

Cited By (1)

Structural origins of the electronic properties of materials via time-resolved infrared spectroscopy Munson, Kyle T.; Kennehan, Eric R.; Asbury, John B. Journal of Materials Chemistry C, Vol. 7, Issue 20 https://doi.org/10.1039/c9tc01348b	journal	January 2019

Similar Records

Solvent-induced excited-state quenching in a chromophore-quencher complex

Journal Article · Thu Mar 22 04:00:00 UTC 1990 · Journal of Physical Chemistry; (USA) · OSTI ID:6547224

Intramolecular charge transfer and thermal exciplex dissociation with p-aminobenzonitriles in toluene

Journal Article · Thu Mar 07 04:00:00 UTC 1991 · Journal of Physical Chemistry; (USA) · OSTI ID:5740970

Ab Initio Multiple Spawning Photochemical Dynamics of DMABN Using GPUs

Journal Article · Thu Dec 15 00:00:00 UTC 2016 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory · OSTI ID:1360220

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Nitrile Vibration Reports Induced Electric Field and Delocalization of Electron in the Charge-Transfer State of Aryl Nitriles

Citation Formats

References (56)

Cited By (1)

Similar Records

Related Subjects