skip to main content

This content will become publicly available on July 21, 2023

Title: High-resolution CH stretch spectroscopy of jet-cooled cyclopentyl radical: First insights into equilibrium structure, out-of-plane puckering, and IVR dynamics
First, high-resolution sub-Doppler infrared spectroscopic results for cyclopentyl radical (C 5 H 9 ) are reported on the α-CH stretch fundamental with suppression of spectral congestion achieved by adiabatic cooling to T rot ≈ 19(4) K in a slit jet expansion. Surprisingly, cyclopentyl radical exhibits a rotationally assignable infrared spectrum, despite 3N − 6 = 36 vibrational modes and an upper vibrational state density (ρ ≈ 40–90 #/cm −1 ) in the critical regime (ρ ≈ 100 #/cm −1 ) necessary for onset of intramolecular vibrational relaxation (IVR) dynamics. Such high-resolution data for cyclopentyl radical permit detailed fits to a rigid-rotor asymmetric top Hamiltonian, initial structural information for ground and vibrationally excited states, and opportunities for detailed comparison with theoretical predictions. Specifically, high level ab initio calculations at the coupled-cluster singles, doubles, and perturbative triples (CCSD(T))/ANO0, 1 level are used to calculate an out-of-plane bending potential, which reveals a C 2 symmetry double minimum 1D energy surface over a C 2v transition state. The inversion barrier [V barrier ≈ 3.7(1) kcal/mol] is much larger than the effective moment of inertia for out-of-plane bending, resulting in localization of the cyclopentyl wavefunction near its C 2 symmetry equilibrium geometry and tunneling splittings more » for the ground state too small (<1 MHz) to be resolved under sub-Doppler slit jet conditions. The persistence of fully resolved high-resolution infrared spectroscopy for such large cyclic polyatomic radicals at high vibrational state densities suggests a “deceleration” of IVR for a cycloalkane ring topology, much as low frequency torsion/methyl rotation degrees of freedom have demonstrated a corresponding “acceleration” of IVR processes in linear hydrocarbons. « less
; ;
Award ID(s):
2053117 1665271
Publication Date:
Journal Name:
The Journal of Chemical Physics
Page Range or eLocation-ID:
Sponsoring Org:
National Science Foundation
More Like this
  1. Highly reactive benzyl radicals are generated by electron dissociative attachment to benzyl chloride doped into a neon–hydrogen–helium discharge and immediately cooled to T rot = 15 K in a high density, supersonic slit expansion environment. The sub-Doppler spectra are fit to an asymmetric-top rotational Hamiltonian, thereby yielding spectroscopic constants for the ground ( v = 0) and first excited ( v = 1, ν 3 , ν 4 ) vibrational levels of the ground electronic state. The rotational constants obtained for the ground state are in good agreement with previous laser induced fluorescence measurements (LIF), with vibrational band origins ( ν 3 = 3073.2350 ± 0.0006 cm −1 , ν 4 = 3067.0576 ± 0.0006 cm −1 ) in agreement with anharmonically corrected density functional theory calculations. To assist in detection of benzyl radical in the interstellar medium, we have also significantly improved the precision of the ground state rotational constants through combined analysis of the ground state IR and LIF combination differences. Of dynamical interest, there is no evidence in the sub-Doppler spectra for tunneling splittings due to internal rotation of the CH 2 methylene subunit, which implies a significant rotational barrier consistent with partial double bond character inmore »the CC bond. This is further confirmed with high level ab initio calculations at the CCSD(T)-f12b/ccpVdZ-f12 level, which predict a zero-point energy corrected barrier to internal rotation of Δ E tun ≈ 11.45 kcal mol −1 or 4005 cm −1 . In summary, the high-resolution infrared spectra are in excellent agreement with simple physical organic chemistry pictures of a strongly resonance-stabilized benzyl radical with a nearly rigid planar structure due to electron delocalization around the aromatic ring.« less
  2. Vibronically resolved laser-induced fluorescence/dispersed fluorescence (LIF/DF) and cavity ring-down (CRD) spectra of the electronic transition of the calcium isopropoxide [CaOCH(CH 3 ) 2 ] radical have been obtained under jet-cooled conditions. An essentially constant energy separation of 68 cm −1 has been observed for the vibrational ground levels and all fundamental vibrational levels accessed in the LIF measurement. To simulate the experimental spectra and assign the recorded vibronic bands, Franck–Condon (FC) factors and vibrational branching ratios (VBRs) are predicted from vibrational modes and their frequencies calculated using the complete-active-space self-consistent field (CASSCF) and equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) methods. Combined with the calculated electronic transition energy, the computational results, especially those from the EOM-CCSD calculations, reproduced the experimental spectra with considerable accuracy. The experimental and computational results suggest that the FC matrix for the studied electronic transition is largely diagonal, but transitions from the vibrationless levels of the à state to the X̃-state levels of the CCC bending ( ν 14 and ν 15 ), CaO stretch ( ν 13 ), and CaOC asymmetric stretch ( ν 9 and ν 11 ) modes also have considerable intensities. Transitions to low-frequency in-plane [ ν 17 ( a ′)] and out-of-planemore »[ ν 30 ( a ′′)] CaOC bending modes were observed in the experimental LIF/DF spectra, the latter being FC-forbidden but induced by the pseudo-Jahn–Teller (pJT) effect. Both bending modes are coupled to the CaOC asymmetric stretch mode via the Duschinsky rotation, as demonstrated in the DF spectra obtained by pumping non-origin vibronic transitions. The pJT interaction also induces transitions to the ground-state vibrational level of the ν 10 ( a ′) mode, which has the CaOC bending character. Our combined experimental and computational results provide critical information for future direct laser cooling of the target molecule and other alkaline earth monoalkoxide radicals.« less
  3. High-resolution direct absorption infrared spectra of metastable cis-formic acid (HCOOH) trapped in a cis-well resonance behind a 15 kcal/mol barrier are reported for the first time, with the energetically unstable conformer produced in a supersonic slit plasma expansion of trans-formic acid/H 2 mixtures. We present a detailed high-resolution rovibrational analysis for cis-formic acid species in the OH stretch ( ν 1 ) fundamental, providing first precision vibrational band origin, rotational constants, and term values, which in conjunction with ab initio calculations at the couple-cluster with single, double, and perturbative triple [CCSD(T)]/ANOn (n = 0, 1, 2) level support the experimental assignments and establish critical points on the potential energy surface for internal rotor trans-to-cis isomerization. Relative intensities for a- and b-type transitions observed in the spectra permit the transition dipole moment components to be determined in the body fixed frame and prove to be in good agreement with ab initio CCSD(T) theoretical estimates but in poor agreement with simple bond-dipole predictions. The observed signal dependence on H 2 in the discharge suggests the presence of a novel H atom radical chemical mechanism for strongly endothermic “up-hill” internal rotor isomerization between trans- and cis-formic acid conformers.
  4. Laser-induced fluorescence (LIF) excitation, dispersed fluorescence (DFL), UV–UV-hole burning, and UV-depletion spectra have been collected on methyl anthranilate (MA, methyl 2-aminobenzoate) and its water-containing complex (MA–H 2 O), under jet-cooled conditions in the gas phase. As a close structural analog of a sunscreen agent, MA has a strong absorption due to the S 0 –S 1 transition that begins in the UV-A region, with the electronic origin at 28 852 cm −1 (346.6 nm). Unlike most sunscreens that have fast non-radiative pathways back to the ground state, MA fluoresces efficiently, with an excited state lifetime of 27 ns. Relative to methyl benzoate, inter-system crossing to the triplet manifold is shut off in MA by the strong intramolecular NH⋯OC H-bond, which shifts the 3 nπ* state well above the 1 ππ* S 1 state. Single vibronic level DFL spectra are used to obtain a near-complete assignment of the vibronic structure in the excited state. Much of the vibrational structure in the excitation spectrum is Franck–Condon activity due to three in-plane vibrations that modulate the distance between the NH 2 and CO 2 Me groups, ν 33 (421 cm −1 ), ν 34 (366 cm −1 ), and ν 36 (179 cm −1more »). Based on the close correspondence between experiment and theory at the TD-DFT B3LYP-D3BJ/def2TZVP level of theory, the major structural changes associated with electronic excitation are evaluated, leading to the conclusion that the major motion is a reorientation and constriction of the 6-membered H-bonded ring closed by the intramolecular NH⋯OC H-bond. This leads to a shortening of the NH⋯OC H-bond distance from 1.926 Å to 1.723 Å, equivalent to about a 25% reduction in the H⋯O distance compared to full H-atom transfer. As a result, the excited state process near the S 1 origin is a hydrogen atom dislocation that is brought about primarily by heavy atom motion, since the shortened H-bond distance results from extensive heavy-atom motion, with only a 0.03 Å increase in the NH bond length relative to its ground state value.« less
  5. Context. Until recently, the 3D shape, and therefore density (when combining the volume estimate with available mass estimates), and surface topography of the vast majority of the largest ( D   ≥ 100 km) main-belt asteroids have remained poorly constrained. The improved capabilities of the SPHERE/ZIMPOL instrument have opened new doors into ground-based asteroid exploration. Aims. To constrain the formation and evolution of a representative sample of large asteroids, we conducted a high-angular-resolution imaging survey of 42 large main-belt asteroids with VLT/SPHERE/ZIMPOL. Our asteroid sample comprises 39 bodies with D   ≥ 100 km and in particular most D   ≥ 200 km main-belt asteroids (20/23). Furthermore, it nicely reflects the compositional diversity present in the main belt as the sampled bodies belong to the following taxonomic classes: A, B, C, Ch/Cgh, E/M/X, K, P/T, S, and V. Methods. The SPHERE/ZIMPOL images were first used to reconstruct the 3D shape of all targets with both the ADAM and MPCD reconstruction methods. We subsequently performed a detailed shape analysis and constrained the density of each target using available mass estimates including our own mass estimates in the case of multiple systems. Results. The analysis of the reconstructed shapes allowed us tomore »identify two families of objects as a function of their diameters, namely “spherical” and “elongated” bodies. A difference in rotation period appears to be the main origin of this bimodality. In addition, all but one object (216 Kleopatra) are located along the Maclaurin sequence with large volatile-rich bodies being the closest to the latter. Our results further reveal that the primaries of most multiple systems possess a rotation period of shorter than 6 h and an elongated shape ( c ∕ a ≤ 0.65). Densities in our sample range from ~1.3 g cm −3 (87 Sylvia) to ~4.3 g cm −3 (22 Kalliope). Furthermore, the density distribution appears to be strongly bimodal with volatile-poor ( ρ ≥ 2.7 g cm −3 ) and volatile-rich ( ρ ≤ 2.2 g cm −3 ) bodies. Finally, our survey along with previous observations provides evidence in support of the possibility that some C-complex bodies could be intrinsically related to IDP-like P- and D-type asteroids, representing different layers of a same body (C: core; P/D: outer shell). We therefore propose that P/ D-types and some C-types may have the same origin in the primordial trans-Neptunian disk.« less