Complete basis set extrapolated potential energy, dipole, and polarizability surfaces of alkali halide ion-neutral weakly avoided crossings with and without applied electric fields

Giese, Timothy J.; York, Darrin M.

doi:10.1063/1.1690232

Cited by 34 publications

(47 citation statements)

References 75 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The DMF of NaCl has been previously studied experimentally by Hebert et al (1968) and de Leeuw et al (1970) using molecular beam electric resonance, and also by carrying out electronic calculations at different levels of theory (Zeiri & Balint-Kurti 1983; Adamowicz & Bartlett 1988; Pluta 2001; Giese & York 2004; Barton et al 2014). In order to get accurate transition intensities, we derived in this work an empirical DMF by direct interpolation of the vibrational dipole moments of the NaCl isotopologues measured by de Leeuw et al (1970) for v = 0, 1, 2, 3 ( 23 Na 35 Cl) and v = 0, 1 ( 23 Na 37 Cl), to the third-order polynomial expansion, μ(r)=μe+μe′(r−re)+μe″(r−re)2/2+μe‴(r−re)3/6, with the dipole moment matrix elements being computed using the HEG calculated variational wave functions.…”

Section: Line Frequencies and Intensities For Naclmentioning

confidence: 99%

HIGH-RESOLUTION ROTATIONAL SPECTRUM, DUNHAM COEFFICIENTS, AND POTENTIAL ENERGY FUNCTION OF NaCl

Cabezas

Cernicharo

Quintana-Lacaci

et al. 2016

ApJ

View full text Add to dashboard Cite

We report laboratory spectroscopy for the first time of the J = 1–0 and J = 2–1 lines of Na35Cl and Na37Cl in several vibrational states. The hyperfine structure has been resolved in both transitions for all vibrational levels, which permit us to predict with high accuracy the hyperfine splitting of the rotational transitions of the two isotopologues at higher frequencies. The new data have been merged with all previous works at microwave, millimeter, and infrared wavelengths and fitted to a series of mass-independent Dunham parameters and to a potential energy function. The obtained parameters have been used to compute a new dipole moment function, from which the dipole moment for infrared transitions up to Δv = 8 has been derived. Frequency and intensity predictions are provided for all rovibrational transitions up to J = 150 and v = 8, from which the ALMA data of evolved stars can be modeled and interpreted.

show abstract

Section: Line Frequencies and Intensities For Naclmentioning

confidence: 99%

HIGH-RESOLUTION ROTATIONAL SPECTRUM, DUNHAM COEFFICIENTS, AND POTENTIAL ENERGY FUNCTION OF NaCl

Cabezas

Cernicharo

Quintana-Lacaci

et al. 2016

ApJ

View full text Add to dashboard Cite

show abstract

“…The ionic and neutral potential energy curves of LiF have been explored in the past by means of FCI, 19 MCSCF, 20 MRCI, 19,21,22 CASPT2, and some of its quasi-degenerate flavors such us D-CASPT2 23 and MS-CASPT2, 24, 25 among other methods. In all these earlier works, special attention has been focused on computing the energy profiles in the region of the ionic-neutral avoided crossing, which represents a hard challenge for any given electronic structure model.…”

Section: A Avoided Crossing In Lif Dissociationmentioning

confidence: 99%

Avoided crossings, conical intersections, and low-lying excited states with a single reference method: The restricted active space spin-flip configuration interaction approach

Casanova

2012

The Journal of Chemical Physics

View full text Add to dashboard Cite

The restricted active space spin-flip CI (RASCI-SF) performance is tested in the electronic structure computation of the ground and the lowest electronically excited states in the presence of near-degeneracies. The feasibility of the method is demonstrated by analyzing the avoided crossing between the ionic and neutral singlet states of LiF along the molecular dissociation. The two potential energy surfaces (PESs) are explored by means of the energies of computed adiabatic and approximated diabatic states, dipole moments, and natural orbital electronic occupancies of both states. The RASCI-SF methodology is also used to study the ground and first excited singlet surface crossing involved in the double bond isomerization of ethylene, as a model case. The two-dimensional PESs of the ground (S(0)) and excited (S(1)) states are calculated for the complete configuration space of torsion and pyramidalization molecular distortions. The parameters that define the state energetics in the vicinity of the S(0)/S(1) conical intersection region are compared to complete active space self-consistent field (CASSCF) results. These examples show that it is possible to describe strongly correlated electronic states using a single reference methodology without the need to expand the wavefunction to high levels of collective excitations. Finally, RASCI is also examined in the electronic structure characterization of the ground and 2(1)A(g)(-), 1(1)B(u)(+), 1(1)B(u)(-), and 1(3)B(u)(-) states of all-trans polyenes with two to seven double bonds and beyond. Transition energies are compared to configuration interaction singles, time-dependent density functional theory (TDDFT), CASSCF, and its second-order perturbation correction calculations, and to experimental data. The capability of RASCI-SF to describe the nature and properties of each electronic state is discussed in detail. This example is also used to expose the properties of different truncations of the RASCI wavefunction and to show the possibility to use an excitation operator with any number of α-to-β electronic promotions.

show abstract

“…For the molecular HamiltonianĤ M , we use a wellparameterized diabatic model of the LiF molecule 63 to investigate the molecule-cavity QED enabled new phenomena. The model contains two diabatic states, the ionic state |I and the covalent state |C , andĤ M in the |I , |C electronic subspace is expressed asĤ…”

Section: The Pauli-fierz Hamiltonianmentioning

confidence: 99%

Polariton Induced Conical Intersection and Berry Phase

Farag¹,

Mandal²,

Huo³

2021

Preprint

View full text Add to dashboard Cite

We investigate the Polariton induced conical intersection (PICI) created from coupling a diatomicmolecule with the quantized photon mode inside an optical cavity, and the corresponding BerryPhase effects. We use the rigorous Pauli-Fierz Hamiltonian to describe the quantum light-matterinteractions between a LiF molecule and the cavity, and exact quantum propagation to investigatethe polariton quantum dynamics. The molecular rotations relative to the cavity polarization directionplay a role as the tuning mode of the PICI, resulting in an effective CI even within a diatomic molecule.To clearly demonstrate the dynamical effects of the Berry phase, we construct two additional modelsthat have the same Born-Oppenheimer surface, but the effects of the geometric phase are removed.We find that when the initial wavefunction is placed in the lower polaritonic surface, the Berryphase causes aπphase-shift in the wavefunction after the encirclement around the CI, indicatedfrom the nuclear probability distribution. On the other hand, when the initial wavefunction is placedin the upper polaritonic surface, the geometric phase significantly influences the couplings betweenpolaritonic states and therefore, the population dynamics between them. These BP effects are furtherdemonstrated through the photo-fragment angular distribution. PICI created from the quantizedradiation field has the promise to open up new possibilities to modulate photochemical reactivities.

show abstract

Complete basis set extrapolated potential energy, dipole, and polarizability surfaces of alkali halide ion-neutral weakly avoided crossings with and without applied electric fields

Cited by 34 publications

References 75 publications

HIGH-RESOLUTION ROTATIONAL SPECTRUM, DUNHAM COEFFICIENTS, AND POTENTIAL ENERGY FUNCTION OF NaCl

HIGH-RESOLUTION ROTATIONAL SPECTRUM, DUNHAM COEFFICIENTS, AND POTENTIAL ENERGY FUNCTION OF NaCl

Avoided crossings, conical intersections, and low-lying excited states with a single reference method: The restricted active space spin-flip configuration interaction approach

Polariton Induced Conical Intersection and Berry Phase

Contact Info

Product

Resources

About