Control of 1,3-Cyclohexadiene Photoisomerization Using Light-Induced Conical Intersections

Kim, Jaehee; Tao, Hairong; White, J. L.; Petrović, Vladimir; Martı́nez, Todd J.; Bucksbaum, P. H.

doi:10.1021/jp208384b

Cited by 104 publications

(115 citation statements)

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“…Because of the presence of several vibrational degrees of freedom, LICIs exist also without rotations and become multidimensional in nuclear coordinate space [12]. This opens the door for manipulating and controlling nonadiabatic effects by light [12][13][14][15][16][17].…”

Section: Introductionmentioning

confidence: 99%

Towards controlling the dissociation probability by light-induced conical intersections

et al. 2016

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Light-induced conical intersections (LICIs) can be formed both by standing or by running laser waves. The position of a LICI is determined by the laser frequency while the laser intensity controls the strength of the nonadiabatic coupling. Recently, it was shown within the LICI framework that linearly chirped laser pulses have an impact on the dissociation dynamics of the D + 2 molecule (J. Chem. Phys. 143, 014305, (2015); ibid 144, 074309, (2016)). In this work we exploit this finding and perform calculations using chirped laser pulses in which the time dependence of the laser frequency is designed so as to force the LICI to move together with the field-free vibrational wave packet as much as possible. Since nonadiabaticity is strongest in the vicinity of the conical intersection, this is the first step towards controlling the dissociation process via the LICI. Our showcase example is again the D + 2 molecular ion. To demonstrate the impact of the LICIs on the dynamical properties of diatomics, the total dissociation probabilities and the population of the different vibrational levels after the dissociation process are studied and discussed.

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Section: Introductionmentioning

confidence: 99%

Towards controlling the dissociation probability by light-induced conical intersections

et al. 2016

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“…The non-adiabatic effects emerging from LICIs should be amenable to control because of possibility to shape the properties of the LICI by laser frequency, duration, intensity, and polarization. The concept of LICIs can also be applied to polyatomic molecules, as shown in a recent laser-induced isomerization experiment [25]. The main difference here compared to the case of diatomic molecules is that several internal nuclear degrees of freedom may be relevant for the formation of the LICI.…”

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confidence: 99%

Observation of Quantum Interferences via Light-Induced Conical Intersections in Diatomic Molecules

et al. 2016

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We observe energy-dependent angle-resolved diffraction patterns in protons from strong-field dissociation of the molecular hydrogen ion H + 2 . The interference is a characteristic of dissociation around a laser-induced conical intersection (LICI), which is a point of contact between two surfaces in the dressed 2-dimensional Born-Oppenheimer potential energy landscape of a diatomic molecule in a strong laser field. The interference magnitude and angular period depend strongly on the energy difference between the initial state and the LICI, consistent with coherent diffraction around a cone-shaped potential barrier whose width and thickness depend on the relative energy of the initial state and the cone apex. These findings are supported by numerical solutions of the time-dependent Schrödinger equation for similar experimental conditions.The Born-Oppenheimer approximation (BOA) represents intramolecular dynamics as the motion of nuclear wave packets on potential energy surfaces (PES) of electronic eigenvalues embedded in the space of nuclear geometries. A molecule on a single PES remains there so long as the adiabatic condition is obeyed, i.e. so long as nuclear kinetic energies are small compared to electronic state separations. This assumption must break down, however, if two or more PESs approach each other [1][2][3]. When this happens non-adiabatic couplings between the nearly-degenerate surfaces become important. The true eigenvalues can then be calculated by diagonalizing the Hamiltonian in the reduced space of the near degeneracy.According to simple geometrical arguments, molecules with at least two dimensions of internal nuclear motion (i.e. three or more atoms) must have some points where two or more PESs become degenerate, a condition known as a conical intersection (CI) [4]. These CIs play a key role in the relaxation dynamics of most polyatomic molecules including important biochemical processes such as the photostability of DNA [5], and the preliminary process of vision [6]. The dimension of the CI manifold is two less than the internal nuclear geometry. Thus for the simplest case of a tri-atomic molecule, the CI manifold has dimensionality of 3N − 8 = 1. The topological nature of CIs allows the nonadiabatic couplings to diverge and thus display related phenomena such as a geometric or Berry's phase [4,7] in wavepackets that circumnavigate the CI.Naturally occurring CIs cannot exist for a free diatomic molecule because the internuclear separation vector R is the only internal nuclear degree of freedom, and this is insufficient to fulfil the crossing condition. The nonadiabatic terms in the full Hamiltonian cause the BOA states to repel according to the so-called "no-crossing" rule. A diatomic molecule in a strong laser field, however, has a second degree of freedom defined by the laser polarization ε. When viewed in a Floquet basis of laserdressed electronic states, a molecule coupled by this field can exhibit a point of degeneracy called a light-induced conical intersection (LICI) in the 2−dimension...

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“…However, recent experiments have shown that it is possible to achieve unprecedented control over photodissociation reactions. [8][9][10] . The LIPs provide a new playground where essentially new electronic states are created and these new chemical species are an open door to control the chemistry of simple molecules or to increase our understanding of the molecular dynamics in excited states.…”

Section: Discussionmentioning

confidence: 99%

“…[109] Although most proposals remain experimentally untested, owing to the difficulty of finding good molecular systems where the strong field interaction is strong enough to generate LIPs, yet not too strong that the ionization is predominant, recent experiments have shown that indeed such control is possible. [8][9][10] In this work, we will review some of our findings. In LightInduced Potentials: Geometrical and Dynamical Features Section, we will provide a simplified analysis of the geometrical and dynamical features of LIPs, outlining the role of the Starkshift and of laser-induced potential energy shaping in several control scenarios.…”

Section: Introductionmentioning

confidence: 98%

“…[7] More recently, the non-resonant strong-field interaction of the pulse provided a means to alter the potential energy surface of the molecule via dynamic Stark effect, "catalyzing" many photochemical processes. [8][9][10][11] While all the previous roles remain useful for different purposes, one can arguably follow this sequence of events as one in which the laser is promoted from the role of a non-specific exciter (and probe of the chemical process), to a reactant and then to a catalyst, using the chemical terminology. In this review, we will outline some of our contributions in the control of molecules in the strong-field regime from a theoretical perspective.…”

Section: Introductionmentioning

confidence: 99%

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Molecular events in the light of strong fields: A light‐induced potential scenario

Chang

Solá

Shin

2016

Int J of Quantum Chemistry

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A new perspective on how to manipulate molecules by means of very strong laser pulses is emerging with insights from the so-called light-induced potentials, which are the adiabatic potential energy surfaces of molecules severely distorted by the effect of the strong field. Different effects appear depending on how the laser frequency is tuned, to a certain electronic transition, creating light-induced avoided crossings, or very off-resonant, generating Stark shifts. In the former case it is possible to induce dramatic changes in the geometry and redistribution of charges in the molecule while the lasers are acting and to fully control photodissociation reactions as well as other photochemical processes. Several theoretical proposals taken from the work of the authors are reviewed and analyzed showing the unique features that the strong-laser chemistry opens to control the transient properties and the dynamics of molecules.

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Control of 1,3-Cyclohexadiene Photoisomerization Using Light-Induced Conical Intersections

Cited by 104 publications

References 60 publications

Towards controlling the dissociation probability by light-induced conical intersections

Towards controlling the dissociation probability by light-induced conical intersections

Observation of Quantum Interferences via Light-Induced Conical Intersections in Diatomic Molecules

Molecular events in the light of strong fields: A light‐induced potential scenario

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