Apparatus and techniques for Fourier transform millimeter-wave spectroscopy
Examples herein include apparatus and techniques that can be used to perform rotational spectroscopy on gas-phase samples. Such techniques can include using a spectrometer providing frequency synthesis and pulse modulation to provide excitation (e.g., pump or probe pulses) of a gas-phase sample at mm-wave frequencies. Synthesis of such mm-wave frequencies can include use of a frequency multiplier, such as an active multiplier chain (AMC). A free induction decay (FID) elicited by the excitation or other time-domain information can be obtained from the sample, such as down-converted and digitized. A frequency domain representation of the digitized information, such as a Fourier transformed representation, can be used to provide a rotational spectrum.
1. A method, comprising:
exciting a gaseous sample using a first pulsed excitation and a second pulsed excitation each including energy in a mm-wave range of frequencies, the first pulsed excitation and the second pulsed excitation spaced apart in time by a specified duration that is varied between respective measurement cycles, and the first and second pulsed excitations generated at least in part using a frequency multiplier to provide the mm-wave range of frequencies;
obtaining respective time-domain representations elicited from the gaseous sample in response to the first and second pulsed excitations corresponding to the respective measurement cycles;
determining a collisional relaxation time constant using the respective time-domain representations of the response; and
estimating a molecular mass of a species included in the gaseous sample at least in part using the determined collisional relaxation time constant.
2. The method of claim 1 , wherein the estimating the molecular mass of the species included in the gaseous sample does not require foreknowledge of the molecular carrier.
3. The method of claim 1 , wherein frequencies of the first and second excitations are different.
4. The method of claim 1 , wherein the frequency multiplier comprises an active multiplier chain.
5. The method of claim 1 , wherein estimating the molecular mass includes obtaining a time-domain representation of a free induction decay of the gaseous sample in response to excitation using the first and second pulsed excitations; and
determining a molecular mass using an analytical model to provide a best fit to an envelope of the free induction decay.
6. The method of claim 1 , wherein the first and second excitations are generated at least in part using a solid-state synthesizer circuit.
7. The method of claim 6 , wherein the solid-state synthesizer circuit includes a first output to provide a first frequency to be upconverted at least in part using the frequency multiplier to provide the first pulsed excitation; and
a second output to provide a second frequency to be upconverted at least in part using the frequency multiplier to provide the second pulsed excitation.
8. The method of claim 6 , wherein the wherein the solid-state synthesizer circuit is configured to provide continuous wave (CW) output; and
wherein the first and second pulsed excitations are provided at least in part by pulse modulating the CW output of the solid-state synthesizer circuit according to a specified modulation pattern defining durations of the first and second pulsed excitations.
9. The method of claim 1 , wherein frequencies of the first and second excitations are specified to provide an integer number of cycles during a measurement period.
10. The method of claim 1 , wherein a frequency of one or more of the first pulsed excitation or the second pulsed excitation is selected at least in part using information obtained from a spectrum obtained via Fourier transformation of a series of obtained time-domain representations of respective responses elicited from the gaseous sample in response to a sequence of pulsed excitations having frequencies offset from one another.
11. The method of claim 10 , wherein the spectrum is obtained at least in part by concatenating a series of Fourier transforms each corresponding to an obtained time-domain response elicited from the gaseous sample in response to a respective pulsed excitation frequency.
12. The method of claim 10 , comprising probing the gaseous sample using a probe frequency selected to modulate an intensity of the observed peak according in response to a presence of a prior excitation of the sample, the prior excitation using a pump frequency that is different from the probe frequency.
13. The method of claim 12 , wherein presence or absence of a species within the gaseous species is determined at least in part using information about whether modulation of the intensity of the observed peak occurs in the presence of the prior excitation.
14. A non-transitory processor-readable medium including instructions that, when performed by a processor circuit, cause an apparatus to:
excite a gaseous sample using pulsed excitations each including energy in a mm-wave range of frequencies, using timing that is varied between respective measurement cycles, the pulsed excitations generated at least in part using a frequency multiplier to provide the mm-wave range of frequencies;
obtain respective time-domain representations elicited from the gaseous sample in response to the pulsed excitation;
determine a collisional relaxation time constant using the respective time-domain representations of the response; and
estimate a molecular mass of a species included in the gaseous sample at least in part using the determined collisional relaxation time constant.
15. The non-transitory processor-readable medium of claim 14 , wherein the instructions to estimate the molecular mass include instructions to:
obtain a time-domain representation of a free induction decay of the gaseous sample; and
determine a molecular mass using an analytical model to provide a best fit to an envelope of the free induction decay.
16. The non-transitory processor-readable medium of claim 14 , wherein frequencies of the pulsed excitations are specified to provide an integer number of cycles during a measurement period.
17. An spectrometer comprising:
a multiplier chain light source including a radio-frequency (RF) input and a mm-wave output;
a frequency source including an output in communication with the RF input of the multiplier chain light source;
a pulse modulator configured to pulse-modulate the output of the frequency source;
a receiver configured to provide a digital representation of a response elicited from a gaseous sample in response to excitation of the gaseous sample, the mm-wave output configured to provide a signal for the excitation; and
a processor circuit configured to:
determine a collisional relaxation time constant using a time-domain representation of the response elicited from the sample; and
estimate a molecular mass of a species included in the gaseous sample at least in part using the determined collisional relaxation time constant;
wherein an output frequency of the frequency source is specified to provide an integral number of oscillation cycles during a measurement cycle, the measurement cycle established at least in part using the pulse modulator.
18. The spectrometer of claim 17 , wherein the frequency source includes at least two outputs having respective output frequencies.
19. The spectrometer of claim 17 , wherein the receiver comprises a dual-conversion superheterodyne circuit configured to down-convert the response elicited from a gaseous sample.
20. The spectrometer of claim 17 , wherein the processor circuit is coupled to the pulse modulator and is configured control the pulse modulator to provide:
a first “pump” excitation pulse having a first specified duration; and
a second “probe” excitation pulse having a second specified duration, and having a specified separation in time from the first “pump” excitation pulse.