Vibrational Energy Redistribution Research Articles

Моделирование и анализ колебательного перераспределения энергии при собственных электромагнитных излучениях в ключевых радиоэлектронных схемах на МОП-транзисторах.

For the first time, a simplified model of the redistribution of vibrational energy in a MOS transistor has been developed and analyzed. The transistor is turned on in open drain mode and in inverter mode. After calculating the parameters, the numerical radio profiles of the signals of the electrical component of electromagnetic radiation, created by the key unit itself, were obtained. An experiment was carried out to register the vibrational redistribution of energy in a MOS transistor using a specially designed sample. The results of registration of a series of radio profiles of signals with the configuration of the universal ports of the sample of a digital device are presented, and a correlation assessment of the reproducibility of the experiment is carried out. The correlation of the radio profiles of the signals obtained as a result of modeling and as a result of the experiment is not lower than 0.93. This testifies to the correctness of the developed models. On the basis of the presented development, a correlation assessment of the radiation of a reference sample and a sample with a slight deviation of parameters has been carried out. Even with a slight change in the parameters of the key node associated with degradation of the gate dielectric, the cross-correlation in the normal state and with a defect r < 0.7, which indicates a significant difference in the signal radio profile of normal functioning and with deterioration of parameters. The proposed models can be used in passive radio-wave technical diagnostics based on the registration of the electrical component of electromagnetic radiation generated by the radio-electronic devices themselves and opens up new possibilities for diagnosing malfunctions at the early stages of their occurrence.

Precise Identification of the Dimethyl Sulfoxide Triggered Tricarbonyldichlororuthenium(II) Dimer for Releasing CO.

Low concentrations of carbon monoxide (CO) can play vital roles in pharmacological and physiological functions in the human body. The transition-metal carbonyl complexes of the tricarbonyldichlororuthenium(II) dimer [Ru2(CO)6Cl4 (CORM-2)] were proposed as CO-releasing molecules (CORMs) to improve the delivery efficiency of CO for therapeutic effects. The accurate identification of final products for CORMs in solution and the detailed mechanisms of the release of CO were the essential prerequisite for its effective physiological application, which have been deficient. In this study, utilizing the cutting-edge two-dimensional (2D) IR spectroscopy, with the intrinsic vibrational modes and the coupling information on dynamics of intramolecular vibrational energy redistribution (IVR), the final products of A, B, C, and E are accurately identified when CORM-2 is dissolved in dimethyl sulfoxide (DMSO). Furthermore, with the clues on intermolecular interaction and chemical exchange dynamics between different products, the transformations between different products are also directly characterized for the first time. These findings challenge the results from the classic 1D spectroscopic pattern, and they evidently demonstrated that the release of CO from CORM-2 in DMSO was slow and complicated with multiple reaction pathways. Combining with DFT simulations, the detailed mechanisms of release of CO for CORM-2 dissolved in DMSO are schematically proposed, which can significantly contribute to its drug optimization and pharmacological as well as physiological applications.

Vibrational energy redistribution in crystalline nitromethane simulated by ab initio molecular dynamics.

Ab initio molecular dynamics simulations (AIMD) are systematically performed to study the Vibrational Energy Redistribution (VER) in solid nitromethane (NM) by combining normal mode decomposition and short-time Fourier transform technique. After the selective excitations of all fourteen intramolecular vibrational modes above 400 cm−1, four three-dimensional (3D) excitation and detected vibrational spectra are obtained. The evolution of the kinetic energy proportion of all vibrations are also given and discussed quantitatively. These results show that, as the daughter modes, NO2 symmetric stretches, CH3 stretches and bends are usually excited quickly and relatively conspicuously compared with the other vibrations. Interestingly, we found that, although the stretching vibration of the CN bond which is a bridge between the methyl and nitro group can not respond immediately to the selective excitations, it always accumulates the vibrational energy slowly and steadily. Then, the underlying mechanisms are discussed based on the response of vibrational modes in both the time and frequency domain. As a result, we found that anharmonic transfers following symmetry rules which involve the couplings assisted by the overtones and rotations, as well as the transfers among the adjacent modes, play important roles in the VER of solid NM.

Ultrafast dynamics of electron excited states of phenylacetylene

Interaction of light with matter has always been important in the field of natural science. Particularly, the ultrafast radiationless relaxation induced by UV light of molecular electronic excited states accompanied by ultrafast energy transfer plays an important role in the natural photophysical, photochemical and biological reactions. Generally, the molecular electronic excited state can be deactivated through a variety of decay channels, including dissociation, isomerization, internal conversion, intersysterm crossing, vibrational energy redistribution, and autoionization. This complexity of relaxation channels brings about a wide variety of deactivation mechanisms. The ultrafast nonadibatic relaxation dynamics of the excited state of phenylacetylene is studied by using femtosecond time-resolved photoelectron imaging and femtosecond time-resolved mass spectrometry. The first excited state S<sub>2</sub> of phenylacetylene is excited by 235 nm pump light, and the excited state deactivation process is detected by 400 nm probe light. The time-dependent curves of parent ions include two exponential curves. One is the fast component with a time constant of 116 fs, and the other is the slow component with a time constant of 106 ps. The time-resolved photoelectron kinetic energy distribution is obtained from the time-resolved photoelectron images. Combined with the time-resolved photoelectron spectroscopy data, the fast component with a time constant of 116 fs is found to reflect the internal conversion process from S<sub>2</sub> state to S<sub>1</sub> state. The experimental results also show that S<sub>1</sub> state is arranged by internal conversion, and the inter system jump process to T<sub>1</sub> state is an important attenuation channel. This work provides a clearer physical picture for S<sub>1</sub> state nonadibatic relaxation dynamics of phenylacetylene.

A general implementation of time-dependent vibrational coupled-cluster theory.

The first general excitation level implementation of the time-dependent vibrational coupled cluster (TDVCC) method introduced in a recent publication [J. Chem. Phys. 151, 154116 (2019)] is presented. The general framework developed for time-independent vibrational coupled cluster (VCC) calculations has been extended to the time-dependent context. This results in an efficient implementation of TDVCC with general coupling levels in the cluster operator and Hamiltonian. Thus, the convergence of the TDVCC[k] hierarchy toward the complete-space limit can be studied for any sum-of-product Hamiltonian. Furthermore, a scheme for including selected higher-order excitations for a subset of modes is introduced and studied numerically. Three different definitions of the TDVCC autocorrelation function (ACF) are introduced and analyzed in both theory and numerical experiments. Example calculations are presented for an array of systems including imidazole, formyl fluoride, formaldehyde, and a reduced-dimensionality bithiophene model. The results show that the TDVCC[k] hierarchy converges systematically toward the full-TDVCC limit and that the implementation allows accurate quantum-dynamics simulations of large systems to be performed. Specifically, the intramolecular vibrational-energy redistribution of the 21-dimensional imidazole molecule is studied in terms of the decay of the ACF. Furthermore, the importance of product separability in the definition of the ACF is highlighted when studying non-interacting subsystems.

State-to-state quantum dynamics of H2O/HOD scattering from Cu(111): Mode- and bond-selective vibrational energy transfer.

Molecular scattering at solid surfaces has been a sensitive probe of the molecule-surface interaction. Existing theoretical studies have primarily focused on diatomic molecules scattering from metal surfaces. Here, we investigate the vibrational state-to-state scattering dynamics of H2O/HOD from Cu(111) by a fully coupled six-dimensional quantum dynamical model based on a first-principles determined potential energy surface. Specifically, state-to-state scattering probabilities of H2O(1ν1) and HOD with its O-H or O-D excitation are obtained in a wide range of incidence energies. We find very efficient ν1-to-ν3 vibrational energy redistribution of H2O, with a similar efficiency to what we found previously for ν3-to-ν1 energy flow in H2O(1ν3) scattering. In comparison, we find that the energy transfer from the more localized 1νOH or 1νOD state to the other bond is much more difficult, in line with the strong bond selectivity observed in the dissociation of HOD on Cu(111). These results suggest that vibrational energy transfer in H2O/HOD scattering from Cu(111) is mode- and bond-selective, which is better described in the sudden limit via a local mode picture. Implications of these results on the mode-specific vibrational energy transfer of other polyatomic molecules scattering from metal surfaces, such as methane and ammonia, have been discussed. We hope that our study will inspire more quantum state-resolved experiments on state-to-state scattering of polyatomic molecules at metal surfaces.

State-to-state methane-surface scattering as a probe of catalytic activity

The paper uses Quantum state-resolved scattering experiment and theory to show that surface-induced intramolecular vibrational energy redistribution in methane-surface scattering is related to the catalytic activity of the impact site.

Tracking asymmetric intramolecular vibrational redistribution of nitromethane

Femtosecond time- and frequency-resolved coherent anti-Stokes Raman scattering (CARS) spectroscopy is proposed to selectively excite parent vibrational modes and detect energy flow to daughter modes in liquid nitromethane (NM, CH3NO2). The NO symmetric bending mode (δsNO2~657cm−1, symmetry: A1), CN symmetric stretching mode (νs(CN)~918cm−1, symmetry: A1), CH3 rocking mode (ρ(CH3)~1104cm−1, symmetry: B1), nitro group stretching modes (νs(NO2)~1379cm−1, symmetry: A1 and νa(NO2)~1560cm−1, symmetry: B1) of nitromethane (NM) are selectively excited in an orderly manner, vibrational energy flow to the neighboring higher ones located outside the excitation range is observed. Counterintuitive up-hill energy flow from lower frequency modes to higher ones is related to the vibrational symmetry. What's more, it is also found that up-hill intramolecular vibrational energy redistribution efficiencies decrease monotonically with the increase of the frequency differences.

Specific Host-Guest Interactions in the Crown Ether Complexes with K+ and NH4+ Revealed from the Vibrational Relaxation Dynamics of the Counteranion.

The specific host-guest interactions in the corresponding complexes of K+ and NH4+ with typical crown ethers were investigated by using FTIR and ultrafast IR spectroscopies. The counteranions, i.e., SCN-, were employed as a local vibrational probe to report the structural dynamics of the complexation. It was found that the vibrational relaxation dynamics of the SCN- was strongly affected by the cations confined in the cavities of the crown ethers. The time constant of the vibrational population decay of SCN- in the complex of NH4+ with the 18-crown-6 was determined to be 6 ± 2 ps, which is ∼30 times faster than that in the complex of K+ with the crown ethers. Control experiments showed that the vibrational population decay of SCN- depended on the size of the cavities of the crown ethers. A theoretical calculation further indicated that the nitrogen atom of SCN- showed preferential coordination to the K+ ions hosted by the crown ethers, while the NH4+ can form hydrogen bonds with the oxygen atoms in the studied crown ethers. The geometric constraints formed in the complex of crown ethers can cause a specific interaction between the NH4+ and SCN-, which can facilitate the intermolecular vibrational energy redistribution of the SCN-.

Elucidating the Coupling Mechanisms of Rapid Intramolecular Vibrational Energy Redistribution in Nitromethane: Ab Initio Molecular Dynamics Simulation.

Ab initio molecular dynamics simulations are presented to investigate the intramolecular vibrational energy redistribution (IVR) of an isolated nitromethane molecule. A number of IVR processes are simulated by monitoring the kinetic energy of vibrational modes under selective low-lying vibrational excitations from their ground states (Δν = 1 or 2). Evolution of the normal-mode kinetic energy gives the ultrafast energy transfer processes from parent modes to daughter modes intuitively. From the ultrafast vibrational transfer made by Fourier transformation of the time-dependent normal-mode kinetic energy, we can capture that the symmetry of the normal modes plays an important role in the anharmonic coupling between the vibrational modes. The results show three symmetry-dependent coupling mechanisms: direct symmetric coupling, overtone-assisted coupling, and rotation-assisted coupling. Furthermore, the calculated efficiencies of IVR also coincide with these mechanisms.

MR-MCTDH[n]: Flexible Configuration Spaces and Nonadiabatic Dynamics within the MCTDH[n] Framework.

Solving the time-dependent Schrödinger equation (TDSE) for large molecular systems is a complicated task due to the inherent exponential scaling of the problem. One of the most successful and versatile methods for obtaining numerically converged solutions for small to medium-sized systems is multiconfiguration time-dependent Hartree (MCTDH). In a recent publication [J. Chem. Phys. 2020, 152, 084101] we introduced a hierarchy of approximations to the MCTDH method which mitigate the exponential scaling by truncating the configuration space based on a maximum excitation level w.r.t. a selected reference configuration. The MCTDH[n] methods are able to treat large systems, but the single-reference Ansatz is not optimal in cases where one (or a few) degrees of freedom are special. Examples could be double-well systems, intramolecular vibrational-energy redistribution (IVR) calculations, or nonadiabatic dynamics. In this work we introduce a multireference (MR) extension to the MCTDH[n] methods where selected higher-order excitations for the special degrees of freedom can be introduced in a simple but flexible way. The resulting MR-MCTDH[n] methods allow for, for example, treating nonadiabatic dynamics within the single-set formalism with the wave packets on each electronic surface described using the same level of approximation. Example calculations are performed on formyl fluoride (IVR), salicylaldimine (double well), and pyrazine (nonadiabatic dynamics). The results show that fast convergence is achieved by extending the configuration space in the special modes that govern the quantum dynamics.

Vibrational energy redistribution during donor-acceptor electronic energy transfer: criteria to identify subsets of active normal modes.

Photoinduced electronic energy transfer in conjugated donor-acceptor systems is naturally accompanied by intramolecular vibrational energy redistributions accepting an excess of electronic energy. Herein, we simulate these processes in a covalently linked donor-acceptor molecular dyad system by using nonadiabatic excited state molecular dynamics simulations. We analyze different complementary criteria to systematically identify the subset of vibrational normal modes that actively participate on the donor → acceptor (S2→ S1) electronic relaxation. We analyze energy transfer coordinates in terms of state-specific normal modes defined according to the different potential energy surfaces (PESs) involved. On one hand, we identify those vibrations that contribute the most to the direction of the main driving force on the nuclei during electronic transitions, represented by the non-adiabatic derivative coupling vector between donor and acceptor electronic states. On the other hand, we monitor normal mode transient accumulations of excess energy and their intramolecular energy redistribution fluxes. We observe that the subset of active modes varies according to the PES on which they belong and these modes experience the most significant rearrangements and mixing. Whereas the nuclear motions that promote donor → acceptor energy funneling can be localized mainly on one or two normal modes of the S2 state, they become spread out across multiple normal modes of the S1 state following the energy transfer event.

Vibrational energy redistribution and vibrational dynamics of methanol mixed with Rhodamine 101 dye

Vibrational energy transfer that occurs after photoexcitation can be tracked in the first several femtoseconds by ultrafast time- and frequency-resolved CARS (coherent anti-Stokes Raman scattering) spectroscopy. Vibrational energy transfer from high-frequency modes to lower ones through chemical bond of pure methanol and methanol/Rhodamine 101 (Rh101) solution is detected. Through comparison and analysis of the experimental results, it is found that surrounding molecules have a significant influence on vibrational energy transfer and vibrational couplings among relevant modes.

High-resolution cavity ring-down spectroscopy of the ν1 + ν6 combination band of methanol at 2.0 μm.

Reported here are portions of the infrared absorption cross section for methanol (CH3OH), as measured by frequency-stabilized cavity ring-down spectroscopy (FS-CRDS) at wavelengths near λ = 2.0 µm. High-resolution spectra of two gravimetric mixtures of CH3OH-in-air with nominal mole fractions of 202.2 µmol/mol and 45.89 µmol/mol, respectively, were recorded at pressures between 0.8 kPa and 102 kPa and at a temperature of 298 K. Covering the experimental wavenumber range of 4990 cm-1 to 5010 cm-1 in increments of 0.0067 cm-1 and with an instrument linewidth of 30 kHz, we observed an evolution in the CH3OH spectrum from resolved absorption lines at a low pressure (0.833 kPa) to a pseudocontinuum of absorption at a near-atmospheric pressure (101.575 kPa). An analysis of resolvable features at the lowest recorded pressure yielded a minimum intramolecular vibrational energy redistribution (IVR) lifetime for the OH-stretch (ν1) plus OH-bend (ν6) combination of τIVR ≥ 232 ps-long compared to other methanol overtones and combinations. Consequently, we show that high-resolution FS-CRDS of this relatively weak CH3OH combination band provided an additional avenue by which to study the intramolecular dynamics of this simplest organic molecule with hindered internal rotation.

Vibrational Energy Redistribution between CH Stretching Modes in Alkyl Chain Monolayers Revealed by Time-Resolved Two-Color Pump-Probe Sum Frequency Spectroscopy.

The vibrational dynamics of the various CH stretching modes in a fatty acid Langmuir-Blodgett film was studied using a resonant narrowband infrared (IR) laser pulse for pumping and a broadband femtosecond IR visible pulse pair for detection in a sum frequency spectroscopy setup. The resulting two-dimensional spectra indicate that pumping either the antisymmetric methyl or methylene stretch results in the transfer of energy to the other modes on a time scale faster than 2 ps. This rapid process is followed by energy redistribution to other modes, presumably the bending and internal rotational modes, with a time constant of approximately 85 ps. The formation of gauche defects is not observed within the first 250 ps. The whole spectrum recovers on a time scale of several nanoseconds, indicating dissipation of the excitation energy into the substrate.

Time series analysis for multi-dimensional dynamical systems combining wavelet transformation and local principal component analysis

Abstract To analyze trajectories for systems of many degrees of freedom, we propose a new method called wavelet local principal component analysis (WlPCA) combining the wavelet transformation and local PCA in time. Our method enables us to reduce the dimensionality of time series both in degrees of freedom and frequency so that characteristic features of oscillatory behavior can be captured. To test the new method, we apply WlPCA to a non-autonomous model of multiple degrees of freedom, the Froeschlé maps of $N=2$ and $N=4$, which correspond to autonomous systems of three and five degrees of freedom, respectively. The eigenvalues and eigenvectors obtained by WlPCA reveal those times when frequency variation exhibits switching between relatively stationary features. Moreover, further analyses indicate which degrees of freedom and frequencies are involved in the switching. We confirm that the switching corresponds to the onset of transport in phase space. These findings imply that, even for systems of larger degrees of freedom, barriers can exist in phase space that block transport for a finite time, thereby dividing the phase space into multiple quasi-stationary regions. Thus, our method is promising for understanding dynamics in systems of many degrees of freedom, such as vibrational-energy redistribution in molecules.

Tuning Molecular Vibrational Energy Flow within an Aromatic Scaffold via Anharmonic Coupling.

From guiding chemical reactivity in synthesis or protein folding to the design of energy diodes, intramolecular vibrational energy redistribution harnesses the power to influence the underlying fundamental principles of chemistry. To evaluate the ability to steer these processes, the mechanism and time scales of intramolecular vibrational energy redistribution through aromatic molecular scaffolds have been assessed by utilizing two-dimensional infrared (2D IR) spectroscopy. 2D IR cross peaks reveal energy relaxation through an aromatic scaffold from the azido- to the cyano-vibrational reporters in para-azidobenzonitrile (PAB) and para-(azidomethyl)benzonitrile (PAMB) prior to energy relaxation into the solvent. The rates of energy transfer are modulated by Fermi resonances, which are apparent by the coupling cross peaks identified within the 2D IR spectrum. Theoretical vibrational mode analysis allowed the determination of the origins of the energy flow, the transfer pathway, and a direct comparison of the associated transfer rates, which were in good agreement with the experimental results. Large variations in energy-transfer rates, approximately 1.9 ps for PAB and 23 ps for PAMB, illustrate the importance of strong anharmonic coupling, i.e., Fermi resonance, on the transfer pathways. In particular, vibrational energy rectification is altered by Fermi resonances of the cyano- and azido-modes allowing control of the propensity for energy flow.

Quasi-Classical Trajectory Study of NH(3∑-) + NH(3∑-) Reactive Collisions.

A full-dimension quasi-classical trajectory study of collisions between two NH radicals is presented. Interatomic interactions are represented by a previously reported global six-dimensional potential energy surface for singlet electronic state of the N2H2 system. This study suggests that the formation of N2 from the collision of two NH radicals may occur via a one-step (NH + NH → N2 + H + H) or two-step (NH + NH → N2H + H → N2 + H + H) microscopic reaction mechanism. A fast vibrational energy redistribution is observed in the four-body complex in the latter mechanism. Excitation functions are presented and discussed. A variant of the vibrational energy quantum mechanical threshold method was used to correct the zero-point energy leakage in the classical calculations. The influence of reactant's rotational and vibrational energy on reactivity was investigated by state-specific calculations with one or both reactants excited. Reaction rate constants for the ground and some rotationally excited states are presented using an Arrhenius-Kooij-like functional form.

Efficient Vibrational Energy Redistribution between Stretching Modes: State-to-State Quantum Scattering of H_{2}O from Cu(111).

State-to-state scattering dynamics of H_{2}O from Cu(111) has been studied by a fully coupled quantum mechanical model which explicitly accounts for the most important molecular degrees of freedom, based on a first-principles determined potential energy surface. When H_{2}O in its antisymmetric O-H stretching vibration (ν_{3}) collides with the surface, we find that the intramolecular vibrational energy redistribution (IVR) is predominant from ν_{3} to the symmetric stretching mode (ν_{1}), while rather inefficient to the bending mode (ν_{2}). This mode-specific IVR results from the strong couplings between stretching modes, which equally dispose the initial energy in ν_{3} into local stretching modes differing by a phase factor. Given the number of stretching modes in H_{2}O and CH_{4}, this mechanism naturally explains why the product ν_{1}/ν_{3} ratio calculated here is ∼3 times over that recently measured for CH_{4} scattering on Ni(111), suggesting that the nonstatistical IVR is more general than expected in polyatomic molecules.

Vibrational coupling effects in the energy redistribution of alkylbenzenes

Ultrafast time- and frequency-resolved coherent anti-Stokes Raman Scattering spectroscopy (CARS) was used to detect vibrational energy redistribution in liquid alkylbenzenes at ambient-temperature. The C–H stretching vibrational modes (vibrational frequencies near ∼3000 cm−1) on substituents were selectively excited, the substituents were CH3 (toluene), (CH3)2CH (isopropylbenzene) and (CH3)3C (t-butylbenzene), vibrational energy flow from the substitution modes to the phenyl modes was observed in the electronic ground state of alkylbenzenes. According to the selective excitation CARS experimental results, beats among these relevant modes were observed and vibrational coupling information was extracted via Fourier analysis. Vibrational coupling and substitution structure that effect energy redistribution processes were discussed.