Brian C. Dian

A broadband Fourier transform microwave spectrometer based on chirped pulse excitation

Designs for a broadband chirped pulse Fourier transform microwave (CP-FTMW) spectrometer are presented. The spectrometer is capable of measuring the 7-18 GHz region of a rotational spectrum in a single data acquisition. One design uses a 4.2 Gsampless arbitrary waveform generator (AWG) to produce a 1 mus duration chirped pulse with a linear frequency sweep of 1.375 GHz. This pulse is sent through a microwave circuit to multiply the bandwidth of the pulse by a factor of 8 and upconvert it to the 7.5-18.5 GHz range. The chirped pulse is amplified by a traveling wave tube amplifier and broadcast inside the spectrometer by using a double ridge standard gain horn antenna. The broadband molecular free induction decay (FID) is received by a second horn antenna, downconverted, and digitized by a 40 Gsampless (12 GHz hardware bandwidth) digital oscilloscope. The second design uses a simplified pulse generation and FID detection scheme, employing current state-of-the-art high-speed digital electronics. In this spectrometer, a chirped pulse with 12 GHz of bandwidth is directly generated by using a 20 Gsampless AWG and upconverted in a single step with an ultrabroadband mixer. The amplified molecular emission is directly detected by using a 50 Gsampless digital oscilloscope with 18 GHz bandwidth. In both designs, fast Fourier transform of the FID produces the frequency domain rotational spectrum in the 7-18 GHz range. The performance of the CP-FTMW spectrometer is compared to a Balle-Flygare-type cavity-FTMW spectrometer. The CP-FTMW spectrometer produces an equal sensitivity spectrum with a factor of 40 reduction in measurement time and a reduction in sample consumption by a factor of 20. The CP-FTMW spectrometer also displays good intensity accuracy for both sample number density and rotational transition moment. Strategies to reduce the CP-FTMW measurement time by another factor of 90 while simultaneously reducing the sample consumption by a factor of 30 are demonstrated.

Measuring Picosecond Isomerization Kinetics via Broadband Microwave Spectroscopy

The rotational spectrum of a highly excited molecule is qualitatively different from its pure rotational spectrum and contains information about the intramolecular dynamics. We have developed a broadband Fourier transform microwave spectrometer that uses chirped-pulse excitation to measure a rotational spectrum in the 7.5- to 18.5-gigahertz range in a single shot and thereby reduces acquisition time sufficiently to couple molecular rotational spectroscopy with tunable laser excitation. After vibrationally exciting a single molecular conformation of cyclopropane carboxaldehyde above the barrier to C–C single-bond isomerization, we applied line-shape analysis of the dynamic rotational spectrum to reveal a product yield and picosecond reaction rate that were significantly different from statistical predictions. The technique should be widely applicable to dynamical studies of radical intermediates, molecular complexes, and conformationally flexible molecules with biological interest.

Conformational isomerization kinetics of pent-1-en-4-yne with 3,330 cm 1 of internal energy measured by dynamic rotational spectroscopy

We demonstrate the application of molecular rotational spectroscopy to measure the conformation isomerization rate of vibrationally excited pent-1-en-4-yne (pentenyne). The rotational spectra of single quantum states of pentenyne are acquired by using a combination of IR–Fourier transform microwave double-resonance spectroscopy and high-resolution, single-photon IR spectroscopy. The quantum states probed in these experiments have energy eigenvalues of ≈3,330 cm−1 and lie above the barrier to conformational isomerization. At this energy, the presence of intramolecular vibrational energy redistribution (IVR) is indicated through the extensive local perturbations found in the high-resolution rotation–vibration spectrum of the acetylenic C–H stretch normal-mode fundamental. The fact that the IVR process produces isomerization is deduced through a qualitatively different appearance of the excited-state rotational spectra compared with the pure rotational spectra of pentenyne. The rotational spectra of the vibrationally excited molecular eigenstates display coalescence between the characteristic rotational frequencies of the stable cis and skew conformations of the molecule. This coalescence is observed for quantum states prepared from laser excitation originating in the ground vibrational state of either of the two stable conformers. Experimental isomerization rates are extracted by using a three-state Bloch model of the dynamic rotational spectra that includes the effects of chemical exchange between the stable conformations. The time scale for the conformational isomerization rate of pentenyne at total energy of 3,330 cm−1 is ≈25 ps and is 50 times slower than the microcanonical isomerization rate predicted by the statistical Rice–Ramsperger–Kassel–Marcus theory.

Motional narrowing of the rotational spectrum of trifluoropropyne at 6550 cm−1 by intramolecular vibrational energy redistribution

We present the basic principles of dynamic rotational spectroscopy for the highly vibrationally excited symmetric top molecule trifluoropropyne (TFP,CF3CCH). Single molecular eigenstate rotational spectra of TFP were recorded in the region of the first overtone of the nu(1) acetylenic stretching mode at 6550 cm(-1) by infrared-pulsed microwave-Fourier transform microwave triple resonance spectroscopy. The average rotational constant (B) of the highly vibrationally mixed quantum states at 6550 cm(-1) is 2909.33 MHz, a value that is 40 MHz larger than the rotational constant expected for the unperturbed C-H stretch overtone (2869.39 MHz). The average rotational constant and rotational line shape of the molecular eigenstate rotational spectra are compared to the distribution of rotational constants expected for the ensemble of normal-mode vibrational states at 6550 cm(-1) that can interact by intramolecular vibrational energy redistribution (IVR). The normal-mode population distribution at 6550 cm(-1) can be described using a Boltzmann distribution with a microcanonical temperature of 1200 K. At this energy the rotational constant distribution in the normal-mode basis set is peaked at about 2910 MHz with a width of about 230 MHz. The distribution is slightly asymmetric with a tail to the high end. The experimentally measured dynamic rotational spectra are centered at the normal-mode distribution peak; however, the spectral width is significantly narrower (40 MHz) than normal-mode ensemble width (230 MHz). This reduction of the width, along with the Lorentzian shape of the eigenstate rotational spectra when compared to the Gaussian shape of the calculated ensemble distribution, illustrates the narrowing of the spectrum due to IVR exchange. The IVR exchange rate was determined to be 120 ps, about ten times faster than the rate at which energy is redistributed from the v=2 level of the acetylenic stretch.

CHIRPED-PULSE FOURIER TRANSFORM MICROWAVE SPECTROSCOPY: A NEW TECHNIQUE FOR RAPID IDENTIFICATION OF CHEMICAL AGENTS

We have developed a new broadband Chirped-Pulse Fourier Transform Microwave (CP-FTMW) spectrometer that allows the microwave spectrum in the 7.5-18.5 GHz range to be measured in a single data event. This technique produces a pure rotational spectrum that can be used for unambiguous identification of any species having a permanent electric dipole moment. CP-FTMW is a gas phase technique that is ideally suited for the detection of airborne chemical warfare agents (CWA) which must be detected in trace amounts (<10 ppm in air). The high resolution of the technique allows the identification of complex mixtures without the need for a preliminary separation step, such as gas chromatography, which significantly reduces analysis time. The technique is “blind” to major atmospheric components (N2, O2, CO2, H2O) as they either do not posses a permanent dipole moment or do not absorb in the range of the spectrometer, thereby eliminating large background signals. In this paper we will present preliminary results that are focused on early detection of airborne CWA, including acquisition time, sensitivity limits, and sample handling requirements for several of these species.