Theory of laser control of vibrational transitions and chemical reactions by ultrashort infrared laser pulses

Korolkov, M. V.; Manz, J.; Paramonov, G. K.

doi:10.1002/9780470141601.ch13

Cited by 17 publications

(5 citation statements)

References 74 publications

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“…The HOD molecule has been a popular prototype for testing different approaches to selective cleaving of bonds [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23] and continues to inspire new schemes for selective control of bond dissociation [17,[20][21][22][23]. The H-OD and HO-D stretching frequencies in HOD are well separated [8,10,11,16,18] and provide for selective excitation of more or less pure O-H and O-D modes [5][6][7][8][10][11][12][13][14][15][16]18,19,22,24,25] in the ground electronic state. The first excited electronic state of HOD is purely repulsive with a saddle point barrier separating the H + O-D and H-O + D channels [26,27].…”

Section: Introductionmentioning

confidence: 99%

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Selective control of HOD photodissociation using low quanta O–D excitation and field optimized initial state (FOIST) based combination of states and colors

Sarma¹,

Adhikari²,

Mishra³

2006

Chemical Physics Letters

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Section: Introductionmentioning

confidence: 99%

“…Use of appropriate IR lasers to achieve selective population of the desired jm, nae vibrational state with m and n quanta of excitation in O-H and O-D modes respectively has been demonstrated by several groups [18,19,22,25] and a mix of excited O-D modes has been used in Ref. [16].…”

Section: Introductionmentioning

confidence: 99%

Selective control of HOD photodissociation using low quanta O–D excitation and field optimized initial state (FOIST) based combination of states and colors

Sarma¹,

Adhikari²,

Mishra³

2006

Chemical Physics Letters

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“…IR laser control of unimolecular reaction dynamics has attracted particular attention from theory (for a recent account, see also ref ). Isomerization reactions, such as the Cope rearrangement in a semibullvalene model or various H atom transfer reactions, were studied as exemplary cases within the development of general control strategies . A common assumption has been that it is possible to excite the RC directly, i.e., without much influence of anharmonic couplings to other coordinates leading to broad absorption bands or competing VER processes.…”

Section: The Reaction Coordinatementioning

confidence: 99%

Infrared Laser Excitation Controlled Reaction Acceleration in the Electronic Ground State

Heyne

Kühn

2019

J. Am. Chem. Soc.

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Propelling a ground state reaction by mode-specific vibrational excitation via infrared (IR) light offers a novel route to carry out ground state chemistry. Here, we describe the acceleration of a bimolecular alcoholysis reaction as a paradigm for IR light-driven ground state reactions. Instead of resorting to coherent control, IR light is used for direct or indirect vibrational excitation of the reaction coordinate (RC) overcoming the activation energy and promoting the ground state reaction with negligible heating of the sample. Thus, knowledge of the RC is crucial to pick the reaction accelerating vibrations. Alternatively, upon mapping the reaction accelerating vibrations an image of the RC can be reconstructed. We discuss the concept of RCs and examine strategies to use vibrational energy relaxation pathways to single out vibrations belonging to the RC. The influence of the solvent interaction and limitations due to conformational heterogeneity are considered. We provide an application example generating microstructures of polymers and address the use for chemical synthesis in general.

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“…The conceptionally simplest approach for IR-driven HT, the pump-dump scheme [45], can be illustrated using a one-dimensional double minimum potential as shown in Fig. 4.1.…”

Section: Laser-driven Intramolecular Hydrogen Transfermentioning

confidence: 99%

Laser‐driven Ultrafast Hydrogen Transfer Dynamics

Kühn

González

2006

Hydrogen‐Transfer Reactions

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The ground state tunnel splitting in a symmetric double well potential, D 0 , is associated with a tunneling time of s 0 ¼ h=2D 0 . If we take the hydrogen transfer (HT) in tropolone [1] as an example we have D 0 » 1 cm -1 and therefore s 0 » 16:7 ps. This is a rather long time as compared, e.g. with the period of an OH-stretch vibration or with the T 1 relaxation time of this vibration in solution [2]. Consequently, to study ultrafast HT in the electronic ground state the dynamics has to be initiated closer to or even above the reaction barrier what could be achieved by an interaction with an IR laser pulse. Of course, this draws on the analogy with electron-vibrational dynamics triggered after almost instantaneous optical excitation and thus switching of the electronic state. Here the driving force for the nuclear wave packet motion after excitation is due to the difference in the electron density which leads, for instance, to the rather rapid reactions observed for excited state HT [3][4][5].Building further on this analogy one could think of adiabatically separating the fast OH-stretch dynamics from the slower motions of the molecular frame. This would result in adiabatic potential energy surfaces (PES) for the slow modes in a given state of the OH-stretch mode [6][7][8]. The HT can then be viewed as a slow mode wave packet moving on the adiabatic potential whose character changes gradually from an OH-stretch excitation localized in the reactant well to an excitation localized in the product well.The first question, which is raised by this simple analogy, concerns the very possibility of exciting slow mode wave packets in a hydrogen bond at all. Taking a different perspective it touches the very issue of interpretation of the notoriously complex IR spectra [9]. In the condensed phase much of this complexity is hidden under bands broadened by the solvent interaction. Hence it was only recently that coherent wave packet motion of a 100 cm -1 hydrogen bond mode could be observed after OH-stretch excitation, although in a system which has only a single minimum potential [10]. Meanwhile coherent low-frequency dynamics has also been observed in a double minimum system (acetic acid dimer) [11]. With this Hydrogen-Transfer Reactions. Edited by

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Theory of laser control of vibrational transitions and chemical reactions by ultrashort infrared laser pulses

Cited by 17 publications

References 74 publications

Selective control of HOD photodissociation using low quanta O–D excitation and field optimized initial state (FOIST) based combination of states and colors

Selective control of HOD photodissociation using low quanta O–D excitation and field optimized initial state (FOIST) based combination of states and colors

Infrared Laser Excitation Controlled Reaction Acceleration in the Electronic Ground State

Laser‐driven Ultrafast Hydrogen Transfer Dynamics

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