Molecular spectroscopy by a Terahertz Time Domain Spectrometer (Hiromichi Hoshina)
1. Introduction
Terahertz is the name of frequency (10
12 Hz), just between infrared and microwave in the electro-magnetic wave,
which has been called "Far Infrared" in past. From the viewpoint
of molecular spectroscopy, a lot of information about molecular
structure and molecular motion can be obtained from the spectra in this
region, such as rotational spectra of light molecules, lower
vibrational spectra carbon chaines, the internal rotational motion of
molecules and intermolecular vibrations.
2.THz-TDS spectrometer
In
our lab. we are focusing on the molecular spectroscopy by a recently
developed Terahertz Time Domain Spectroscopy (THz-TDS). Since
THz-TDS is more sensitive and more stable than conventional FT-IR
spectrometer, we expect to make more accurate measurement by using our
system.
In THz-TDS system, transient change of the electric field
made by a femto second laser (pulse width = ~100 fs) is used as a THz
wave source, and the change of the pulse shape after passing through
the sample is detected. In our system, the production and
extinction of carriers on the biased photo-conductive antenna make
transient change of the electric field, and the time profile of the
electric field is detected on by a probe pulse with changing the
detecting timing which was scanned by a optical delay stage.
The
obtained waveform of the electric field is then Fourier transformed to
the frequency domain power spectrum. The spectra below show the
example of the THz time domain waveform with and without sample (H
2O
500 Pa). Due to the coherent rotational motion of the sample, the
time domain wave form shows structure after main pulse, called "free
induction decay (FID)". After Fourier Transform, these FID are
transformed to the absorption lines in the frequency domain spectra.
The
table below shows comparison of conventional spectroscopic apparatus
with THz-TDS. Compared to the continuous wave light sources such
as Tu-FIR and BWOs, THz-TDS has no advantage for high resolution
spectroscopy. However, for the spectroscopy in lower resolution,
it can make more accurate measurement of line shape and line intensity
in better S/N ratio than FT-IR.
| CW laser, BWO | FT-IR | THz-TDS |
周波数分解能 | ~MHz | ~100 MHz | 1GHz |
測定範囲 | ~10 THz | ~100 THz以上 | ~4.0 THz |
光源のパワー | mW ~ nW | mW | mW |
検出器 | Si Bolometer / InSb Detector (4K) | EO/ 光伝導アンテナ (300K) |
NEP@3THz | 10-9 ~10-10 W・Hz1/2 | ~10-16 W・Hz1/2 |
ダイナミックレンジ | | ~103 | ~108 |
S/N | | ○ | ◎ |
光源の安定性 | | ○ | ◎ |
変調した検出 | ◎ | △ | △ |
実験の容易さ | × | ○ | ◎ |
3. Pressure broadening parameters of rotational lines of water vapor
As
one of the application of THz-TDS for molecular spectroscopy, we
measured precise pressure broadening parameters of water vapor.
THz
spectroscopy of the planets in the solar system will provide important
information for the planetary science because gases at those
temperatures usually have emission peaks in the THz region. For
example, the accurate calculation of the pressure broadening of the
transitions of the water vapor is important in the estimation of the
Earth thermal balance (actually 60 % of thermal radiation is due to
water vapor).
For
the measurement of pressure broadening parameters, FT-IR has been used
previously, because Fourier Transform spectrometer can measure many
lines in wide frequency region simultaneously. THz-TDS enables
more accurate measurement of water vapor line shapes than FT-IR by its
good S/N ratio.
The figure below shows the obtained parameters.
Compared to the values from HITRAN database, our parameters show 10%
smaller values.