Energy Transport In Molecules Research Articles

Ballistic and diffusive vibrational energy transport in molecules.

Energy transport in molecules is essential for many areas of science and technology. Strong covalent bonds of a molecular backbone can facilitate the involvement of the molecule's high-frequency modes in energy transport, which, under certain conditions, makes the transport fast and efficient. We discuss such conditions and describe various transport regimes in molecules, including ballistic, diffusive, directed diffusion, and intermediate regime cases, in light of recently developed experimental and theoretical approaches.

Vibrational energy transport in molecules and the statistical properties of vibrational modes

Statistical properties of the eigenmodes computed for two molecules, dodecane and perfluorododecane, are examined and compared with predictions of random matrix theory. The eigenmode statistics of the heat carrying modes of perfluorododecane correspond to Porter-Thomas statistics, whereas those for dodecane do not. Vibrational energy transport in the two molecules is also computed and found to be diffusive in perfluorododecane but not in dodecane, consistent with recent experiments. The correspondence between eigenmode statistics and vibrational energy transport dynamics in molecules as well as thermalization in molecules are discussed.

Shape, orientation and magnitude of the curl quantum flux, the coherence and the statistical correlations in energy transport at nonequilibrium steady state

We provide a quantitative description of the nonequilibriumness based on the model of coupled oscillators interacting with multiple energy sources. This can be applied to the study of vibrational energy transport in molecules. The curl quantum flux quantifying the nonequilibriumness and time-irreversibility is quantified in the coherent representation and we find the geometric description of the shape and polarization of the flux which provides the connection between the microscopic description of quantum nonequilibriumness and the macroscopic observables, i.e., correlation function. We use the Wilson loop integral to quantify the magnitude of curl flux, which is shown to be correlated to the correlation function as well. Coherence contribution is explicitly demonstrated to be non-trivial and to considerably promote the heat transport quantified by heat current and efficiency. This comes from the fact that coherence effect is microscopically reflected by the geometric description of the flux. To uncover the effect of vibron–phonon coupling between the vibrational modes of molecular stretching (vibron) and the molecular chain (phonon), we further explore the influences of localization, which leads to the coherent and incoherent regimes that are characterized by the current–current correlations.

Band-selective ballistic energy transport in alkane oligomers: toward controlling the transport speed.

Intramolecular transport of vibrational energy in two series of oligomers featuring alkane chains of various length was studied by relaxation-assisted two-dimensional infrared spectroscopy. The transport was initiated by exciting various end-group modes (tags) such as different modes of the azido (ν(N≡N) and ν(N═N)), carboxylic acid (ν(C═O)), and succinimide ester (νas(C═O)) with short mid-IR laser pulses. It is shown that the transport via alkane chains is ballistic and the transport speed is dependent on the type of the tag mode that initiates the transport. The transport speed of 8.0 Å/ps was observed when initiated by either ν(C═O) or νas(C═O). When initiated by ν(N≡N) and ν(N═N), the transport speed of 14.4 ± 2 and 11 ± 4 Å/ps was observed. Analysis of the vibrational relaxation channels of different tags, combined with the results for the group velocity evaluation, permits identification of the chain bands predominantly contributing to the transport for different cases of the transport initiation. For the transport initiated by ν(N≡N) the CH2 twisting and wagging chain bands were identified as the major energy transport channels. For the transport initiated by ν(C═O), the C-C stretching and CH2 rocking chain bands served as major energy transporters. The transport initiated by ν(N═N) results in direct formation of the wave packet within the CH2 twisting and wagging chain bands. These developments can aid in designing molecular systems featuring faster and more controllable energy transport in molecules.

Room-temperature ballistic energy transport in molecules with repeating units.

In materials, energy can propagate by means of two limiting regimes: diffusive and ballistic. Ballistic energy transport can be fast and efficient and often occurs with a constant speed. Using two-dimensional infrared spectroscopy methods, we discovered ballistic energy transport via individual polyethylene chains with a remarkably high speed of 1440 m/s and the mean free path length of 14.6 Å in solution at room temperature. Whereas the transport via the chains occurs ballistically, the mechanism switches to diffusive with the effective transport speed of 130 m/s at the end-groups attached to the chains. A unifying model of the transport in molecules is presented with clear time separation and additivity among the transport along oligomeric fragments, which occurs ballistically, and the transport within the disordered fragments, occurring diffusively. The results open new avenues for making novel elements for molecular electronics, including ultrafast energy transporters, controlled chemical reactors, and sub-wavelength quantum nanoseparators.

Vibrational energy transport in molecules studied by relaxation-assisted two-dimensional infrared spectroscopy.

This review presents an overview of the relaxation-assisted two-dimensional infrared (RA 2DIR) spectroscopy method for measuring structures and energy transport dynamics in molecules. The method strongly enhances the range of accessible distances compared to traditional 2DIR and offers new structural reporters, such as the energy transport time, cross-peak amplification factors, and connectivity patterns. The use of the method for assigning vibrational modes with various levels of delocalization is illustrated. RA 2DIR relies on vibrational energy transport in molecules; as such, the transport mechanism can be conveniently studied by the method. Applications to identify diffusive and ballistic energy transport are demonstrated.

Vibrational and coherence dynamics of molecules.

We analytically investigate the population and coherence dynamics and relaxations in the vibrational energy transport in molecules. The corresponding two time scales t1 and t2 are explored. Coherence-population entanglement is found to considerably promote the time scale t2 for dephasing and the amplitude of coherence. This is attributed to the suppression of the environment-induced drift force by coherence. Moreover the population imbalance (magnetization) is shown to be significantly amplified with the coherence-population entanglement. Contrary to the previous studies, we exactly elucidate a coherent process by showing t1 < t2. We predict the relaxation of vibrational and orientational dynamics of OH-stretching modes in agreement with the recent experiments, when applied to the water molecules dissolved in D2O. Finally we explore the coherence effect on the heat current at the macroscopic level.

Constant-speed vibrational signaling along polyethyleneglycol chain up to 60-Å distance

A series of azido-PEG-succinimide ester oligomers with a number of repeating PEG units of 0, 4, 8, and 12 (azPEG0, 4, 8, and 12) was investigated using a relaxation-assisted two-dimensional infrared (RA 2DIR) spectroscopy method. The RA 2DIR method relies on the energy transport in molecules and is capable of correlating the frequencies of vibrational modes separated by large through-bond distances. Excitation of the azido group in the compounds at ca. 2,100 cm(-1) generates an excess energy which propagates in the molecule as well as dissipates into the solvent. We discovered that a part of the excess energy propagates ballistically via the covalent backbone of the molecules with a constant speed of ca. 550 m/s. The transport is described as a propagation of a vibrational wavepacket having a mean-free-path length of 10-15 Å. The discovery has the potential for developing new efficient signal transduction strategies for molecular electronics and biochemistry. It also permits extending the distances accessible in RA 2DIR structural measurements up to ca. 60 Å.

Relaxation-Assisted Two-Dimensional Infrared (RA 2DIR) Method: Accessing Distances over 10 Å and Measuring Bond Connectivity Patterns

Development of new approaches for measuring three-dimensional structures and dynamics of structural changes is important for a number of natural sciences, including structural biology, where it can lead to understanding the physical bases of molecular recognition and catalysis. A two-dimensional infrared (2DIR) spectroscopy method permits measuring pairwise interactions among vibrational modes in molecules providing a molecular scale ruler for delivering structural constraints, such as the distances between the vibrational modes, angles between their transition dipoles, and the energy-transfer rates between them. While there is a large variety of systems that have recently been interrogated using 2DIR, questions remain of how to measure structural features of larger molecules. The challenges of working with larger molecules, such as proteins, include very congested vibrational spectra, a small range of distances accessible by the 2DIR method, and sensitivity issues. This Account describes the efforts of our laboratory to overcome some of these challenges. First, we discuss the dual-frequency 2DIR approach, which provides the highest selectivity to a particular pair of vibrational reporters and highest sensitivity. Second, we describe our steps in developing vibrational labels, novel for 2DIR, such as C identical withN and C-D stretching modes that have frequencies in the water transparency region, as well as the modes in the fingerprint region. The schemes suitable for labeling amino acids are discussed. Next, we describe the novel relaxation-assisted 2DIR (RA 2DIR) method, developed in our laboratory. The method uses vibrational relaxation and vibrational energy transport in molecules and the thermalization process on a molecular scale, to generate stronger cross-peaks. An 18-fold cross-peak amplification was observed for the modes separated by about 11 A using the RA 2DIR method, and larger amplifications are expected for larger distances between the modes. Large amplification provided by the RA 2DIR method enhances the sensitivity of 2DIR spectroscopy and permits longer range structural measurements. In addition to generating stronger cross-peaks, a correlation of the energy transport time with the intermode distance is demonstrated. This correlation permits measurements of mode-connectivity patterns in molecules much similar to those available in total correlation spectroscopy (TOCSY) and heteronuclear multiple-bond correlation (HMBC) methods of 2D nuclear magnetic resonance (NMR) spectroscopy. It is our hope that, with a proper calibration, the RA 2DIR method will permit speedy assessments of distances and the bond connectivity patterns in molecules and reach the level of an analytical method.

Bond connectivity measured via relaxation-assisted two-dimensional infrared spectroscopy

The relaxation-assisted two-dimensional infrared (RA 2DIR) method is a novel technique for probing structures of molecules, which relies on vibrational energy transport in molecules. In this article we demonstrate the ability of RA 2DIR to detect the bond connectivity patterns in molecules using two parameters, a characteristic intermode energy transport time (arrival time) and a cross-peak amplification coefficient. A correlation of the arrival time with the distance between the modes is demonstrated. An 18-fold amplification of the cross-peak amplitude for the modes separated by approximately 11 A is shown using RA 2DIR; larger cross-peak amplifications are expected for the modes separated by larger distances. The RA 2DIR method enhances the applicability of 2DIR spectroscopy by making practical the long-range measurements using a variety of structural reporters, including weak IR modes. The data presented demonstrate the analytical power of RA 2DIR which permits the speedy structural assessments of the bond connectivity patterns.