Vibrational Transition Dipole Research Articles

Ab initio spectroscopic studies of AlF and AlCl molecules

In this work, we report the results from our spectroscopic study on AlF and AlCl molecules. We carry out detailed electronic structure calculations in both the molecules, including obtaining the potential energy surfaces of the [Formula: see text] ground electronic state and some of the low-lying excited electronic states belonging to [Formula: see text] and [Formula: see text] symmetries. This is followed by evaluating the spectroscopic constants and molecular properties such as electric dipole moments and electric quadrupole moments. Throughout, we employ the multi-reference configuration interaction method and work with high-quality quadruple zeta basis sets. Further, transition dipole moments between the ground electronic state and singlet excited states are also studied. The relevant vibrational parameters are computed by solving the vibrational Schrödinger equation. Subsequently, the vibrational energy spacings and transition dipole moments between the vibrational levels belonging to the same electronic states are used to evaluate the spontaneous and black-body radiation-induced transition rates, followed by computing the lifetimes. Finally, the energy differences between rotational levels belonging to different vibrational levels and within an electronic state as well as the Einstein coefficients are reported.

Molecular factors determining brightness in fluorescence-encoded infrared vibrational spectroscopy.

Fluorescence-encoded infrared (FEIR) spectroscopy is a recently developed technique for solution-phase vibrational spectroscopy with detection sensitivity at the single-molecule level. While its spectroscopic information content and important criteria for its practical experimental optimization have been identified, a general understanding of the electronic and nuclear properties required for highly sensitive detection, i.e., what makes a molecule a "good FEIR chromophore," is lacking. This work explores the molecular factors that determine FEIR vibrational activity and assesses computational approaches for its prediction. We employ density functional theory (DFT) and its time-dependent version (TD-DFT) to compute vibrational and electronic transition dipole moments, their relative orientation, and the Franck-Condon factors involved in FEIR activity. We apply these methods to compute the FEIR activities of normal modes of chromophores from the coumarin family and compare these predictions with experimental FEIR cross sections. We discuss the extent to which we can use computational models to predict the FEIR activity of individual vibrations in a candidate molecule. The results discussed in this work provide the groundwork for computational strategies for choosing FEIR vibrational probes or informing the structure of designer chromophores for single-molecule spectroscopic applications.

Vibrational Dipole-Dipole Coupling and Long-Range Forces between Macromolecules.

Long-range interactions between biomacromolecules are considered important for directing intracellular processes. Recent studies have posited that interactions between oscillating dipoles are well-suited to mediating long-range forces because they are weakly screened by a dielectric environment. Here, we extend these studies and present a quantum electrodynamic mechanism for resonant interactions between vibrational transition dipole moments of molecules. We explicitly consider the molecular charge density oscillations as IR transition dipoles. This gives a physical, molecular assignment to the idea of oscillating dipoles and allows us to develop explicit expressions for the interactions that can be quantified using parameters known from experiment. Moreover, in the same framework, we can describe van der Waals forces. We use numerical calculations to estimate the strength of resonant vibrational dipole-dipole interactions over long distances and compare these estimates to the van der Waals interaction. We find that the resonant vibrational dipole-dipole interactions dominate over the long range.

New acetylene line list near 3.8-μm - Part III - 12C13CH2 and 12C2HD

The intensities of minor acetylene isotopologues 12C13CH2 and 12C2HD have been studied from Fourier transform spectra of acetylene in natural abundance using high optical path length. This study completes the work performed in the two first paper of the series (JQSRT 2023;295:108,413 and JQSRT 2023;311:108,771) where 71 bands of 12C2H2 were studied in the ΔP = 4 spectral region (∼2400–2900 cm−1). In this work, 692 measured line intensities allowed to derive vibrational transition dipole moment squared (and sometimes Herman-Wallis coefficients) for 11 bands of 12C13CH2 and 6 bands of 12C2HD. Using line positions and broadening parameters from literature, a line list has been generated for atmospheric and astrophysical applications.

Electron transfer rate modulation with mid-IR in butadiyne-bridged donor-bridge-acceptor compounds.

Controlling electron transfer (ET) processes in donor-bridge-acceptor (DBA) compounds by mid-IR excitation can enhance our understanding of the ET dynamics and may find practical applications in molecular sensing and molecular-scale electronics. Alkyne moieties are attractive to serve as ET bridges, as they offer the possibility of fast ET and present convenient vibrational modes to perturb the ET dynamics. Yet, these bridges introduce complexity because of the strong torsion angle dependence of the ET rates and transition dipoles among electronic states and a shallow torsion barrier. In this study, we implemented ultrafast 3-pulse laser spectroscopy to investigate how the ET from the dimethyl aniline (D) electron donor to the N-isopropyl-1,8-napthalimide (NAP) electron acceptor can be altered by exciting the CC stretching mode (νCC) of the butadiyne bridge linking the donor and acceptor. The electron transfer was initiated by electronically exciting the acceptor moiety at 400 nm, followed by vibrational excitation of the alkyne, νCC, and detecting the changes in the absorption spectrum in the visible spectral region. The experiments were performed at different delay times t1 and t2, which are the delays between UV-mid-IR and mid-IR-Vis pulses, respectively. Two sets of torsion-angle conformers were identified, one featuring a very fast mean ET time of 0.63 ps (group A) and another featuring a slower mean ET time of 4.3 ps (group B), in the absence of the mid-IR excitation. TD-DFT calculations were performed to determine key torsion angle dependent molecular parameters, including the electronic and vibrational transition dipoles, transition frequencies, and electronic couplings. To describe the 3-pulse data, we developed a kinetic model that includes a locally excited, acceptor-based S2 state, a charge separated S1 state, and their vibrationally excited counterparts, with either excited νCC (denoted as S1Atr, S1Btr, S2Atr, and S2Btr, where tr stands for the excited triplet bond, νCC) or excited daughter modes of the νCC relaxation (S1Ah, S1Bh, S2Ah, and S2Bh, where h stands for vibrationally hot species). The kinetic model was solved analytically, and the species-associated spectra (SAS) were determined numerically using a matrix approach, treating first the experiments with longer t1 delays and then using the already determined SAS for modeling the experiments with shorter t1 delays. Strong vibronic coupling of νCC and of vibrationally hot states makes the analysis complicated. Nevertheless, the SAS were identified and the ET rates of the vibrationally excited species, S2Atr, S2Btr and S2Bh, were determined. The results show that the ET rate for the S2A species is ca. 1.2-fold slower when the νCC mode is excited. The ET rate for species S2B is slower by ca. 1.3-fold if the compound is vibrationally hot and is essentially unchanged when the νCC mode is excited. The SAS determined for the tr and h species resemble the SAS for their respective precursor species in the 2-pulse transient absorption experiments, which validates the procedure used and the results.

Theoretical study of the spin-orbit coupled molecular states of the Mg-He dimer.

The primary objective of this study is to conduct precise ab initio calculations of the spin-orbit interaction between Mg and He atoms. Our investigation centers on identifying the first low-lying electronic states of the Mg-He molecule through high-level theoretical methods such as CCSD(T) and RCCSD(T) and SA-CASSCF/MRCI, while also integrating Davidson and BSSE corrections to refine our findings further. Additionally, we employ the state-interacting method to comprehensively account for the influence of spin-orbit coupling (SO) on molecular states. We carefully characterize the potential energy curves (PECs) of these molecular states by deriving crucial spectroscopic parameters including Re, De, Be and Te, which are then compared against data from prior studies. Moreover, our analysis extends to evaluating vibrational levels, radiative lifetimes, and transition dipole moments (TDMs), offering a comprehensive understanding of the system's dynamics. Notably, we locate the positions of satellite features within the absorption spectra of brown and white dwarfs. To validate the precision and reliability of our findings, extensive comparisons are made with both theoretical predictions and experimental observations, ensuring robustness and accuracy in our conclusions.

LED-based Fourier transform spectroscopy of 14N216O in the 9750-12050 cm−1 region

The five bands of the nitrous oxide molecule (ν1+4ν3,ν1+4ν20+3ν3, 3ν1+3ν3, ν1+5ν3 and 6ν1+2ν3) were studied in the 9750–12,050 cm−1 region using a Bruker IFS-125 M Fourier Transform Spectrometer. High brightness LEDs used as the light sources, which have provided a high signal-to-noise ratio and made it possible to record weak lines with intensities of the order of 1 × 10−26 cm/molecule at 296 K. Each spectrum was obtained by averaging over 33,120 scans. The line parameters (centers and intensities) were recovered from the observed spectra. The spectroscopic constants of the upper vibrational states together with the vibrational transition dipole moments were fitted to the measured line positions and intensities, respectively. It was found that the ν1+5ν3 band is in an interpolyad resonance anharmonic interaction with the 6ν1+2ν3 band.

Multimode vibrational dynamics and orientational effects in fluorescence-encoded infrared spectroscopy. II. Analysis of early-time signals.

Developing fluorescence-encoded infrared (FEIR) vibrational spectroscopy for single-molecule applications requires a detailed understanding of how the molecular response and external experimental parameters manifest in the detected signals. In Paper I [L. Whaley-Mayda, A. Guha, and A. Tokmakoff, J. Chem. Phys. 159, 194201 (2023)] we introduced a nonlinear response function theory to describe vibrational dynamics, vibronic coupling, and transition dipole orientation in FEIR experiments with ultrashort pulses. In this second paper, we apply the theory to investigate the role of intermode vibrational coherence, the orientation of vibrational and electronic transition dipoles, and the effects of finite pulse durations in experimental measurements. We focus on measurements at early encoding delays-where signal sizes are largest and therefore of most value for single-molecule experiments, but where many of these phenomena are most pronounced and can complicate the appearance of data. We compare experiments on coumarin dyes with finite-pulse response function simulations to explain the time-dependent behavior of FEIR spectra. The role of the orientational response is explored by analyzing polarization-dependent experiments and their ability to resolve relative dipole angles in the molecular frame. This work serves to demonstrate the molecular information content of FEIR experiments, and develop insight and guidelines for their interpretation.

Multimode vibrational dynamics and orientational effects in fluorescence-encoded infrared spectroscopy. I. Response function theory.

Fluorescence-encoded infrared (FEIR) spectroscopy is an emerging technique for performing vibrational spectroscopy in solution with detection sensitivity down to single molecules. FEIR experiments use ultrashort pulses to excite a fluorescent molecule's vibrational and electronic transitions in a sequential, time-resolved manner, and are therefore sensitive to intervening vibrational dynamics on the ground state, vibronic coupling, and the relative orientation of vibrational and electronic transition dipole moments. This series of papers presents a theoretical treatment of FEIR spectroscopy that describes these phenomena and examines their manifestation in experimental data. This first paper develops a nonlinear response function description of Fourier-transform FEIR experiments for a two-level electronic system coupled to multiple vibrations, which is then applied to interpret experimental measurements in the second paper [L. Whaley-Mayda et al., J. Chem. Phys. 159, 194202 (2023)]. Vibrational coherence between pairs of modes produce oscillatory features that interfere with the vibrations' population response in a manner dependent on the relative signs of their respective Franck-Condon wavefunction overlaps, leading to time-dependent distortions in FEIR spectra. The orientational response of population and coherence contributions are analyzed and the ability of polarization-dependent experiments to extract relative transition dipole angles is discussed. Overall, this work presents a framework for understanding the full spectroscopic information content of FEIR measurements to aid data interpretation and inform optimal experimental design.

The first observation of the 12C16O2 absorption bands near 660 nm

The absorption spectra of carbon dioxide were recorded in the region from 15,000 to 15,300 cm−1, using a Bruker IFS 125 HR Fourier transform spectrometer and a 30 m multipass cell with the White type optical system. The recording was performed at a spectral resolution of 0.044 – 0.050 cm−1, room temperature, a path length of 1057.95 m and pressures of 185 and 362 mbar. Utilization of a LED as a light source provided a sensitivity (noise equivalent absorption) at the level of kν = 1.23 × 10-10 cm−1 and allowed detection of a number of lines of two 3005i − 00001 (i = 2,3) bands and several lines of the 60031 – 00001 band of 12C16O2 with the intensity values down to 10-30 cm−1/(molecule cm−2) at 296 K. These bands were observed for the first time. The uncertainty of the line position measurements was estimated to be about 0.005 cm−1 for the unblended lines with a high signal-to-noise ratio. The uncertainties of the retrieved line intensities for the strongest unblended lines are at the level of 15 %. The spectroscopic constants for observed bands were fitted to the observed line positions. The vibrational transition dipole moments squared of these bands were fitted to the observed line intensities. The measured line positions were compared to those from the HITRAN2020 database and to those predicted with the global effective Hamiltonian. The measured line intensities were compared to the values from the HITRAN2020 database and from the Ames2021 line list.

High sensitivity absorption spectroscopy of acetylene near 760 nm

The Cavity Ring-Down Spectra (CRDS) of acetylene were recorded in the 13,087–13,300 cm−1 range with the sensitivity of 3.4 × 10−11 cm−1. Four cold and six hot bands of 12C2H2 were assigned in these spectra. Only five of them were observed before. The ν1+3ν3+ν41 band is the strongest one lying in this region. The line positions and intensities were recovered from the recorded spectra. The line intensities in this region are reported for the first time. The line positions were modeled using the traditional power series expression in terms of the angular momentum quantum number for an isolated band. The line intensities were modeled using the vibrational transition dipole moment squared and the Herman-Wallis parameters.

Orientational Coupling of Molecules at Interfaces Revealed by Two-Dimensional Electronic-Vibrational Sum Frequency Generation (2D-EVSFG).

Photoinduced relaxation processes at interfaces are intimately related to many fields such as solar energy conversion, photocatalysis, and photosynthesis. Vibronic coupling plays a key role in the fundamental steps of the interface-related photoinduced relaxation processes. Vibronic coupling at interfaces is expected to be different from that in bulk due to the unique environment. However, vibronic coupling at interfaces has not been well understood due to the lack of experimental tools. We have recently developed a two-dimensional electronic-vibrational sum frequency generation (2D-EVSFG) for vibronic coupling at interfaces. In this work, we present orientational correlations in vibronic couplings of electronic and vibrational transition dipoles as well as the structural evolution of photoinduced excited states of molecules at interfaces with the 2D-EVSFG technique. We used malachite green molecules at the air/water interface as an example, to be compared with those in bulk revealed by 2D-EV. Together with polarized VSFG and ESHG experiments, polarized 2D-EVSFG spectra were used to extract relative orientations of an electronic transition dipole and vibrational transition dipoles at the interface. Combined with molecular dynamics calculations, time-dependent 2D-EVSFG data have demonstrated that structural evolutions of photoinduced excited states at the interface have different behaviors than those in bulk. Our results showed that photoexcitation leads to intramolecular charge transfer but no conical interactions in 25 ps. Restricted environment and orientational orderings of molecules at the interface are responsible for the unique features of vibronic coupling.

The absorption bands of 12C16O2 near 718 nm

The absorption spectra of carbon dioxide were recorded in the region from 13,500 to 14,200 cm−1, using a Bruker IFS 125 HR Fourier transform spectrometer and a 30 m multipass cell with the White type optical system. The recording was performed at spectral resolution of 0.03–0.04 cm−1, room temperature, path length of 1057.95 m and at three pressures of 252, 403 and 582 mbar. The achieved sensitivity (noise equivalent absorption) at the level of kν = 6 × 10−10 cm−1 allowed detection of a number of lines of three 2005i - 00001 (i = 1,2,3) bands of 12C16O2 with the intensity values down to 10−29 cm−1/(molecule cm−2) at 296 K. The 20053–00001 band was observed for the first time. The line intensities for all bands were measured for the first time. The uncertainty of the line position measurements was estimated to be about 0.007 cm−1 for the unblended lines with a high value of the signal-to-noise ratio. The uncertainties of the retrieved line intensities for the strongest unblended lines are on the level of 10%. The spectroscopic constants for the three observed bands were fitted to the observed line positions. The vibrational transition dipole moments squared of these bands were fitted to the observed line intensities. A comparison of the measured line positions to those from the HITRAN2020 database was done. Finally a comparison of the measured line intensities to those contained in the HITRAN2020 database as well as in the new version of the Ames line list was also given.

Design of an Electrostatic Frequency Map for the NH Stretch of the Protein Backbone and Application to Chiral Sum Frequency Generation Spectroscopy.

We develop an electrostatic map for the vibrational NH stretch (amide A) of the protein backbone with a focus on vibrational chiral sum frequency generation spectroscopy (chiral SFG). Chiral SFG has been used to characterize protein secondary structure at interfaces using the NH stretch and to investigate chiral water superstructures around proteins using the OH stretch. Interpretation of spectra has been complicated because the NH stretch and OH stretch overlap spectrally. Although an electrostatic map for water OH developed by Skinner and co-workers was used previously to calculate the chiral SFG response of water structures around proteins, a map for protein NH that is directly responsive to biological complexity has yet to be developed. Here, we develop such a map, linking the local electric field to vibrational frequencies and transition dipoles. We apply the map to two protein systems and achieve much better agreement with experiment than was possible in our previous studies. We show that couplings between NH and OH vibrations are crucial to the line shape, which informs the interpretation of chiral SFG spectra, and that the chiral NH stretch response is sensitive to small differences in structure. This work increases the utility of the NH stretch in biomolecular spectroscopy.

Temperature Dependence of Non-Condon Effects in Two-Dimensional Vibrational Spectroscopy of Water.

Non-Condon effects in vibrational spectroscopy refers to the dependence of a molecule's vibrational transition dipole and polarizability on the coordinates of the surrounding environment. Earlier studies have shown that such effects can be pronounced for hydrogen-bonded systems like liquid water. Here, we present a theoretical study of two-dimensional vibrational spectroscopy under the non-Condon and Condon approximations at varying temperatures. We have performed calculations of both two-dimensional infrared and two-dimensional vibrational Raman spectra to gain insights into the temperature dependence of non-Condon effects in nonlinear vibrational spectroscopy. The two-dimensional spectra are calculated for the OH vibration of interest in the isotopic dilution limit where the coupling between the oscillators is ignored. Generally, both the infrared and Raman line shapes undergo red shifts with decrease in temperature due to strengthening of hydrogen bonds and decrease in the fraction of OH modes with weaker or no hydrogen bonds. The infrared line shape is further red-shifted under the non-Condon effects at a given temperature, while the Raman line shape does not show any such red shift due to non-Condon effects. The spectral dynamics becomes slower on decrease of temperature due to slower hydrogen bond relaxation and, for a given temperature, the spectral diffusion occurs at a faster rate upon inclusion of non-Condon effects. The time scales of spectral diffusion extracted from different metrics agree well with each other and also with experiments. The changes in the spectrum due to non-Condon effects are found to be more significant at lower temperatures.

Quantum-chemical calculation of two-dimensional infrared spectra using localized-mode VSCF/VCI.

Computational protocols for the simulation of two-dimensional infrared (2D IR) spectroscopy usually rely on vibrational exciton models which require an empirical parameterization. Here, we present an efficient quantum-chemical protocol for predicting static 2D IR spectra that does not require any empirical parameters. For the calculation of anharmonic vibrational energy levels and transition dipole moments, we employ the localized-mode vibrational self-consistent field (L-VSCF)/vibrational configuration interaction (L-VCI) approach previously established for (linear) anharmonic theoretical vibrational spectroscopy [P. T. Panek and C. R. Jacob, ChemPhysChem 15, 3365-3377 (2014)]. We demonstrate that with an efficient expansion of the potential energy surface using anharmonic one-mode potentials and harmonic two-mode potentials, 2D IR spectra of metal carbonyl complexes and dipeptides can be predicted reliably. We further show how the close connection between L-VCI and vibrational exciton models can be exploited to extract the parameters of such models from those calculations. This provides a novel route to the fully quantum-chemical parameterization of vibrational exciton models for predicting 2D IR spectra.

Elucidating Λ-doublet splittings and rotational quantum number-dependent collisional broadenings in 2∏1/2 and 2∏3/2 spin-split sub-bands of NO at 5.2 µm

High-resolution ro-vibrational spectroscopic features of nitric oxide (NO) are particularly interesting because of the unpaired electron and non-zero nuclear spin of the nitrogen atom. Here, ultra-sensitive cavity ring-down spectroscopy (CRDS) coupled with an external-cavity quantum cascade laser (EC-QCL) radiation source was employed to measure the rotationally-resolved fine structure Λ-doublet splittings between the parity doublet e and f components in the (2∏1/2 - 2∏1/2) and (2∏3/2 - 2∏3/2) allowed sub-bands of the v = 1 ← 0 fundamental vibrational band of NO molecule near 5.2 µm. Subsequently, we determined several principal spectroscopic parameters such as the Λ-doubling constants, vibrational transition dipole moments and the Herman-Wallis coefficients for both e and f Λ-doublet components by probing various R-branch rotational lines (J = 0.5 to 23.5) of the studied spin-split sub-bands of NO associated with spin–orbit interaction. In addition, we performed the pressure broadening effect on the Λ-doublet splittings in collision with three vital perturbing gases at room temperature (296 K) and accurately determined the pressure broadening coefficients, γi (e,f) in cm-1atm−1 [(i = He, Ar and Zero air (mainly N2 + O2)] along with their dependence on the rotational quantum number (J). We observed the pronounced collision-induced rotational quantum effect and the result of rotationally inelastic collision in the system for each collision partner. All these measured high-resolution new spectroscopic parameters over 33 ro-vibrational transitions via an EC-QCL based CRDS method will help significantly in interpreting fundamental molecular properties of this diatomic NO molecule.

High sensitivity absorption spectroscopy of acetylene near 770 nm

The Cavity Ring-Down Spectra (CRDS) of acetylene were recorded in the 12933–13087 cm−1 region with sensitivity of 2 × 10−11 cm−1. Six bands of 12C2H2 and one band of 12C13CH2 were assigned in these spectra. The 3ν1+ν3 band is the strongest one lying in this region. The line positions and intensities were recovered from the recorded spectra. The line intensities in this region are reported for the first time. The line positions were modeled using the traditional power series expression in terms of the angular momentum quantum number for an isolated band. The line intensities were modeled using the vibrational transition dipole moment squared and the Herman-Wallis parameters. The recommended line list of acetylene was prepared for the 12887–13084 cm−1 region. It is based on the calculated line parameters. But in the case of the perturbations, the calculated line parameters are substituted by the observed ones. The harmonic basis state compositions of the upper states of the two bands at 12991.08 and 12988.75 cm−1 were considered in detail.

Sub-optical-cycle light-matter energy transfer in molecular vibrational spectroscopy

The evolution of ultrafast-laser technology has steadily advanced the level of detail in studies of light-matter interactions. Here, we employ electric-field-resolved spectroscopy and quantum-chemical modelling to precisely measure and describe the complete coherent energy transfer between octave-spanning mid-infrared waveforms and vibrating molecules in aqueous solution. The sub-optical-cycle temporal resolution of our technique reveals alternating absorption and (stimulated) emission on a few-femtosecond time scale. This behaviour can only be captured when effects beyond the rotating wave approximation are considered. At a femtosecond-to-picosecond timescale, optical-phase-dependent coherent transients and the dephasing of the vibrations of resonantly excited methylsulfonylmethane (DMSO2) are observed. Ab initio modelling using density functional theory traces these dynamics back to molecular-scale sample properties, in particular vibrational frequencies and transition dipoles, as well as their fluctuation due to the motion of DMSO2 through varying solvent environments. Future extension of our study to nonlinear interrogation of higher-order susceptibilities is fathomable with state-of-the-art lasers.

Study of the Experimental and Simulated Vibrational Spectra Together with Conformational Analysis of Thioether Cyanobiphenyl-Based Liquid Crystal Dimers.

Infrared spectroscopy (IR) and quantum chemistry calculations that are based on the density functional theory (DFT) have been used to study the structure and molecular interactions of the nematic and twist-bend phases of thioether-linked dimers. Infrared absorbance measurements were conducted in a polarized beam for a homogeneously aligned sample in order to obtain more details about the orientation of the vibrational transition dipole moments. The distributions to investigate the structure and conformation of the molecule dihedral angle were calculated. The calculated spectrum was compared with the experimental infrared spectra and as a result, detailed vibrational assignments are reported.