Enhanced alignment and orientation of polar molecules by vibrational resonant adiabatic passage

The authors show that polar molecules can be adiabatically aligned and oriented by laser pulses more efficiently when the laser frequencies are vibrationally resonant. The aligned molecules are found in a superposition of vibrational pendular states, each associated with the alignment of the rotor in one vibrational state. The authors construct the dressed potential associated with this mechanism. Values of detunings and field amplitudes are given to optimize the degree of alignment and orientation for the CO molecule.     

Molecular orientation of a model liquid crystal alignment layer

An analytical methodology, involving the use of a combination of second harmonic generation (SHG) and linear dichroism, was utilized to probe the molecular orientation and angular distribution of a model liquid crystal (LC) alignment layer. In order to determine which film structure would be best suited for use as an alignment layer, the azo dye o-methyl red (MR) was covalently bound to a glass substrate using both monofunctional and trifunctional silane chemistry. The influence of solvent on the orientation and angular distribution of both thin films was also investigated. For the monofunctional silane film under water, the mean orientation angle of the MR molecular long axis was 67±4° and the width of an assumed Gaussian distribution was 32±2°. Under hexanes, the mean orientation angle was the same within error (63±1°) but the distribution width narrowed considerably to 22±1°. Molecular orientation within the trifunctional silane film exhibited little dependence on solvent. Under water, the mean orientation angle and angular distribution width were 76±3° and 30±1°, respectively. With hexanes as the solvent, the mean orientation angle and angular distribution width were 79±1° and 30±1°, respectively. Orientation insensitive SHG measurements indicated that surface coverage in the tri-functional silane film was twice that in the mono-functional silane film. The observed orientational differences were attributed to differences in the forces that dictate molecular orientation for the two systems. Based on the higher orientation angle, higher surface coverage and the lack of solvent dependence, MR-tri exhibits more desirable characteristics for use as an LC alignment layer.     

Reduced density matrix hybrid approach: an efficient and accurate method for adiabatic and non-adiabatic quantum dynamics

We present a new approach to calculate real-time quantum dynamics in complex systems. The formalism is based on the partitioning of a system's environment into "core" and "reservoir" modes with the former to be treated quantum mechanically and the latter classically. The presented method only requires the calculation of the system's reduced density matrix averaged over the quantum core degrees of freedom which is then coupled to a classically evolved reservoir to treat the remaining modes. We demonstrate our approach by applying it to the spin-boson problem using the noninteracting blip approximation to treat the system and core, and Ehrenfest dynamics to treat the reservoir. The resulting hybrid methodology is accurate for both fast and slow baths, since it naturally reduces to its composite methods in their respective regimes of validity. In addition, our combined method is shown to yield good results in intermediate regimes where neither approximation alone is accurate and to perform equally well for both strong and weak system-bath coupling. Our approach therefore provides an accurate and efficient methodology for calculating quantum dynamics in complex systems.     

Theoretical study of determining orientation and alignment of symmetric top molecule using laser-induced fluorescence

General expressions used for extracting the orientation and alignment parameters of a symmetric top molecule from laser-induced fluorescence (LIF) intensity are derived by employing the density matrix approach. The molecular orientation and alignment are described by molecular state multipoles. Excitation and detection are circularly and linearly polarized lights, respectively. In general cases, the LIF intensity is a complex function of the initial molecular state multipoles, the dynamic factors and the excitation-detection geometrical factors. It contains a population, ten orientation and fourteen alignment multipoles. The problem of how to extract the initial molecular state multipoles from the resolved LIF intensity is discussed.     

A proposal to measure atomic alignment and orientation parameters using laser photon deflection

In this paper, it is pointed out that the optical force which an atom experiences when excited by near-resonant laser light can under certain conditions depend not only on the atomic energy sublevel populations, but also on the horizontal coherences between the sublevels. A theoretical investigation of this behaviour is presented and a novel technique is proposed for applying photon deflection of atoms to the measurement of atomic collision alignment and orientation parameters.     

Vibrationally selective optimal control of alignment and orientation using infrared laser pulses: application to carbon monoxide

Optimal control methods are used to study molecular alignment and orientation using infrared laser pulses. High order molecule-field interactions are taken into account through the use of the electric-nuclear Born-Oppenheimer approximation [G. G. Balint-Kurti et al., J. Chem. Phys. 122, 084110 (2005)]. High degrees of alignment and orientation are achieved by optimized infrared laser pulses of duration on the order of one rotational period of the molecule. It is shown that, through the incorporation of a vibrational projection operator into the optimization procedure, it is possible not only to maximize the alignment and orientation but also to bring the whole system into a single prescribed vibrational manifold. Numerical calculations are performed for carbon monoxide using ab initio potential energies computed in the presence of external electric fields.     

An analytic representation of the radial dependence of adiabatic and non-adiabatic corrections from molecular spectra of diatomic molecules

A method of determining the radial dependence of the adiabatic and non-adiabatic corrections contributing to the spectroscopie parameters Δ^a,b_kl of diatomic molecules according to an analytic representation is proposed. The method is applied to HCl and CO, and results for LiH are compared with published data.     

Analysis of collisional alignment and orientation studied by scattering of spin-polarized electrons from laser excited atoms

A general framework using density matrices is developed for the analysis of atomic excitation by spin-polarized electrons. This framework is applied to the specific case of the 3S _1/2→3P _3/2 transition in Na, as studied by the time-reversed, superelastic process. The scattering is characterized in terms of physical parameters describing the collisionally excitedp-state, i.e., its angular momentum (L _⊥), linear polarization (P _lin), and alignment angle (γ), with these parameters defined separately for singlet and triplet excitation. An expression for the scattering intensity is derived which is valid for arbitrary electron polarization and atomic state preparation. Specific examples are discussed with a view toward complete determination of the relevant scattering amplitudes and phases. Recent experimental results are reevaluated for comparison with theoretical calculations, and suggestions are made for future experiments.     

Coherent and incoherent orientation and alignment of ICN photoproducts

We report extended measurements of the rotational polarization and correlated angular distribution of CN photofragments from ICN photodissociation, with a particular emphasis on the creation and detection of molecular orientation with circularly-polarized light. Doppler profiles of the nascent photoproducts are measured by Frequency-Modulated (FM) transient absorption, and the resulting high signal-to-noise data are valuable for verifying the form of the angular correlations between the recoil velocity, the photofragment rotational angular momentum, and the space-fixed frame defined by the dissociation polarization. A space-fixed bipolar moment notation can be used for an unambiguous characterization of the maximal set of polarization properties that can be created with one-photon excitation and detected with one-photon Doppler-resolved absorption spectroscopy. Relating the observed polarization moments to the various coherent and incoherent, adiabatic and non-adiabatic mechanisms, that have been derived and verified extensively in the case of diatomic photodissociation to polarized atomic fragments, is not unambiguous in the case of diatomic fragments from triatomic precursors. Constraints among various polarization moments confirmed in the case of diatomic dissociation are not confirmed in this triatomic case, where the perpendicular transitions to non-degenerate A' and A' components of a linear Omega = 1 state are qualitatively different from excitation to degenerate Omega = +/-1 states in a diatomic molecule.     

Quantum study of electronically non-adiabatic collinear reactions. I. Hyperspherical description of the electronuclear dynamics

The hyperspherical close-coupling formalism is applied to the study of triatomic collinear chemical reactions involving electronically non-adiabatic transitions. We propose the use of hyperspherical coordinates in the complex zone and of locally adapted Jacobi coordinates in the fragmentation zones. Matching procedures, allowing the switch from one representation to the other, are described. The possibility of long-range electrovibrational couplings is considered. Possible simplifications in the practical implementation of the formalism are examined.     

Theoretical study of the absorption and emission spectrum and non-adiabatic excited state dynamics of gas-phase xanthone

The ground, singlet, and triplet excited state structures (S₁, S₂, T₁, and T₂) of xanthone have been calculated and characterized in the adiabatic representation by using time-dependent density functional theory (TDDFT). However, the fast intramolecular transition mechanisms of xanthone are still under debate, and so we perform non-adiabatic excited state dynamics of the photochemistry of xanthone gas phase and find that it follows El-Sayed's rule. Electronic transition mechanism of xanthone is sequential from the S₂ state: the singlet internal conversion (IC) time from S₂ (¹ππ*) to S₁ (¹nπ*) is 3.85 ps, the intersystem crossing (ISC) from S₁ (¹nπ*) to T₂ (³ππ*) takes 4.76 ps, and the triplet internal conversion from T₂ (³ππ*) to T₁ (³nπ*) takes 472 fs. The displaced oscillator, Franck–Condon approximation, and one-photon excitation equations were used to simulate the absorption spectra of S₀ → S₂ transition, with v₅₅ being most crucial for S₀ structure; the fluorescence spectra of S₁ → S₀ transition with v₄₇ for S₁; and the phosphorescence spectra of T₁ → S₀ transition with v₄ for T₁. Our method can reproduce the experimental absorption, fluorescence, and phosphorescence spectra of gas-phase xanthone.     

An adiabatic local model for the internal structure of charge-transfer excitons: Dimers and trimers

In charge-transfer crystals, the exciton-phonon interaction significantly influences the internal structure of charge-transfer excitons (CTEs). The formation of CTE dimers and trimers is considered in an adiabatic non-centrosymmetric model which includes phonon dispersion. Changes of lattice frequencies near the CTE are analysed.     

Theoretical model for the wetting of a rough surface

Many applications would benefit from an understanding of the physical mechanism behind fluid movement on rough surfaces, including the movement of water or contaminants within an unsaturated rock fracture. Presented is a theoretical investigation of the effect of surface roughness on fluid spreading. It is known that surface roughness enhances the effects of hydrophobic or hydrophilic behavior, as well as allowing for faster spreading of a hydrophilic fluid. A model is presented based on the classification of the regimes of spreading that occur when fluid encounters a rough surface: microscopic precursor film, mesoscopic invasion of roughness and macroscopic reaction to external forces. A theoretical relationship is developed for the physical mechanisms that drive mesoscopic invasion, which is used to guide a discussion of the implications of the theory on spreading conditions. Development of the analytical equation is based on a balance between capillary forces and frictional resistive forces. Chemical heterogeneity is ignored. The effect of various methods for estimating viscous dissipation is compared to available data from fluid rise on roughness experiments. Methods that account more accurately for roughness shape better explain the data as they account for more surface friction; the best fit was found for a hydraulic diameter approximation. The analytical solution implies the existence of a critical contact angle that is a function of roughness geometry, below which fluid will spread and above which fluid will resist spreading. The resulting equation predicts movement of a liquid invasion front with a square root of time dependence, mathematically resembling a diffusive process.     

Spectroscopy of low-energy non-adiabatic resonances in photodissociation to open-shell atoms: CH+, a model system

Theoretical calculations of the low-energy CH⁺ photodissociation spectrum display extremely complicated structure due to strong non-adiabatic couplings which are present when molecules dissociate to open-shell atoms. An analysis of the spectrum, using methods which will be explained elsewhere, leads to general principles for describing the resonances. These principles should be of aid in assigning experimental CH⁺ photodissociation spectra and those of other systems with strong non-adiabatic interactions.     

Theoretical study of LiK and LiK+ in adiabatic representation

The potential energy curves have been calculated for the electronic states of the molecule LiK within the range 3 to 300 a.u., of the internuclear distance R. Using an ab initio method, through a semiempirical spin-orbit pseudo-potential for the Li (1s ²) and K (1s ²2s ²2p ⁶3s ²3p ⁶) cores and core valence correlation correction added to the electrostatic Hamiltonian with Gaussian basis sets for both atoms. The core valence effects including core-polarization and core-valence correlation are taken into account by using an l-dependent core-polarization potential. The molecular orbitals have been derived from self-consistent field (SCF) calculation. The spectroscopic constants, dipole moments and vibrational levels of the lowest electronic states of the LiK molecule dissociating into K (4s, 4p, 5s, 3d, and 5p) + Li (2s, 2p, 3s, and 3p) in ^{1, 3}Σ, ^{1, 3}Π, and ^{1, 3}Δ symmetries. Adiabatic results are also reported for ²Σ, ²Π, and ²Δ electronic states of the molecular ion LiK⁺ dissociating into Li (2s, 2p, 3s, and 3p) + K⁺ and Li⁺ + K (4s, 4p, 5s, 3d, and 5p). The comparison of the present results with those available in the literature shows a very good agreement in spectroscopic constants of some lowest states of the LiK and LiK⁺ molecules, especially with the available theoretical works. The existence of numerous avoided crossing between electronic states of ²Σ and ²Π symmetries is related to the charge transfer process between the two ionic systems Li⁺K and LiK⁺.     

Time-dependent density-functional theory beyond the adiabatic approximation: insights from a two-electron model system

Most applications of time-dependent density-functional theory (TDDFT) use the adiabatic local-density approximation (ALDA) for the dynamical exchange-correlation potential V(xc)(r,t). An exact (i.e., nonadiabatic) extension of the ground-state LDA into the dynamical regime leads to a V(xc)(r,t) with a memory, which causes the electron dynamics to become dissipative. To illustrate and explain this nonadiabatic behavior, this paper studies the dynamics of two interacting electrons on a two-dimensional quantum strip of finite size, comparing TDDFT within and beyond the ALDA with numerical solutions of the two-electron time-dependent Schrodinger equation. It is shown explicitly how dissipation arises through multiple particle-hole excitations, and how the nonadiabatic extension of the ALDA fails for finite systems but becomes correct in the thermodynamic limit.