Probing the Structure, Pseudorotation, and Radial Vibrations of Cyclopentane by Femtosecond Rotational Raman Coherence Spectroscopy

Femtosecond time-resolved Raman rotational coherence spectroscopy (RCS) is employed to determine accurate rotational, vibration–rotation coupling constants, and centrifugal distortion constants of cyclopentane (C⁵H¹⁰). Its lowest-frequency vibration is a pseudorotating ring deformation that interconverts 10 permutationally distinct but energetically degenerate “twist” minima interspersed by 10 “bent” conformers. While the individual twist and bent structures are polar asymmetric tops, the pseudorotation is fast on the time scale of external rotation, rendering cyclopentane a fluxionally nonpolar symmetric top molecule. The pseudorotational level pattern corresponds to a one-dimensional internal rotor with a pseudorotation constant Bps ≈ 2.8 cm⁻¹. The pseudorotational levels are significantly populated up to l = ± 13 at 298 K; <10% of the molecules are in the l = 0 level. The next-higher vibration is the “radial” ν²³ ring deformation mode at 273 cm⁻¹, which is far above the pseudorotational fundamental. Femtosecond Raman RCS measurements were performed in a gas cell at T = 293 K and in a pulsed supersonic jet at T ≈ 90 K. The jet cooling reduces the pseudorotational distribution to l < ±8 and eliminates the population of ν²³, allowing one to determine the rotational constant as A0 = B0 = 6484.930(11) MHz. This value is ∼300 times more precise than the previous value. The fit of the RCS transients reveals that the rotation–pseudorotation coupling constant αe,psB = −0.00070(1) MHz is diminutive, implying that excitation of the pseudorotation has virtually no effect on the B0 rotational constant of cyclopentane. The smallness of αe,psB can be realized when comparing to the vibration–rotation coupling constant of the ν²³ vibration, αe,23B = −9.547(1) MHz, which is about 10⁴ times larger.

MOREMATA: Stata module (Mata) to provide various functions

This package includes various Mata functions. kern(): various kernel functions; kint(): kernel integral functions; kdel0(): canonical bandwidth of kernel; quantile(): quantile function; median(): median; iqrange(): inter-quartile range; ecdf(): cumulative distribution function; relrank(): grade transformation; ranks(): ranks/cumulative frequencies; freq(): compute frequency counts; histogram(): produce histogram data; mgof(): multinomial goodness-of-fit tests; collapse(): summary statistics by subgroups; _collapse(): summary statistics by subgroups; gini(): Gini coefficient; sample(): draw random sample; srswr(): SRS with replacement; srswor(): SRS without replacement; upswr(): UPS with replacement; upswor(): UPS without replacement; bs(): bootstrap estimation; bs2(): bootstrap estimation; bs_report(): report bootstrap results; jk(): jackknife estimation; jk_report(): report jackknife results; subset(): obtain subsets, one at a time; composition(): obtain compositions, one by one; ncompositions(): determine number of compositions; partition(): obtain partitions, one at a time; npartitionss(): determine number of partitions; rsubset(): draw random subset; rcomposition(): draw random composition; colvar(): variance, by column; meancolvar(): mean and variance, by column; variance0(): population variance; meanvariance0(): mean and population variance; mse(): mean squared error; colmse(): mean squared error, by column; sse(): sum of squared errors; colsse(): sum of squared errors, by column; benford(): Benford distribution; cauchy(): cumulative Cauchy-Lorentz dist.; cauchyden(): Cauchy-Lorentz density; cauchytail(): reverse cumulative Cauchy-Lorentz; invcauchy(): inverse cumulative Cauchy-Lorentz; rbinomial(): generate binomial random numbers; cebinomial(): cond. expect. of binomial r.v.; root(): Brent's univariate zero finder; nrroot(): Newton-Raphson zero finder; finvert(): univariate function inverter; integrate_sr(): univariate function integration (Simpson's rule); integrate_38(): univariate function integration (Simpson's 3/8 rule); ipolate(): linear interpolation; polint(): polynomial inter-/extrapolation; plot(): Draw twoway plot; _plot(): Draw twoway plot; panels(): identify nested panel structure; _panels(): identify panel sizes; npanels(): identify number of panels; nunique(): count number of distinct values; nuniqrows(): count number of unique rows; isconstant(): whether matrix is constant; nobs(): number of observations; colrunsum(): running sum of each column; linbin(): linear binning; fastlinbin(): fast linear binning; exactbin(): exact binning; makegrid(): equally spaced grid points; cut(): categorize data vector; posof(): find element in vector; which(): positions of nonzero elements; locate(): search an ordered vector; hunt(): consecutive search; cond(): matrix conditional operator; expand(): duplicate single rows/columns; _expand(): duplicate rows/columns in place; repeat(): duplicate contents as a whole; _repeat(): duplicate contents in place; unorder2(): stable version of unorder(); jumble2(): stable version of jumble(); _jumble2(): stable version of _jumble(); pieces(): break string into pieces; npieces(): count number of pieces; _npieces(): count number of pieces; invtokens(): reverse of tokens(); realofstr(): convert string into real; strexpand(): expand string argument; matlist(): display a (real) matrix; insheet(): read spreadsheet file; infile(): read free-format file; outsheet(): write spreadsheet file; callf(): pass optional args to function; callf_setup(): setup for mm_callf().