Rovibrational Characterization of High-Lying Electronic States of Cu2
by Double-Resonant Nonlinear Spectroscopy
knowledge of the electronically excited states of the copper dimer is
limited. This is common for transition metals, as the high density of
states hinders both experimental assignment and computation. In this
work, two-color resonant four-wave mixing spectroscopy was applied to
neutral Cu2 in the gas phase. The method yielded accurate
positions of individual rovibrational lines in the I-X and J-X
electronic systems. This revealed the term symbols for the I and J
states as 1Πu (1u) and 1Σ+u
(0+u), respectively. For the 63Cu2
isotopologue, accurate molecular constants were obtained. The
characterization of the J state finally allowed decisive
determination of its electron configuration. The J state is obtained
from the ground state by promotion of a 3dπg electron into the
weakly bonding 4pπu molecular orbital. From the data
analysis, lifetimes of the I state (between 10 ps and 5 ns) and J
state (66 ns) were inferred.
TC-RFWM spectra of
the I-X and J-X transitions of 63Cu2. The pump
wavelength was scanned over the bands of interest while a single
rotational line in the B-X (1-0) band (green label P(J")) was
probed. The inset illustrates this scheme that reduces the observed
spectra to lines originating from a defined rotational level J"
of the ground state (X, v = 0). For comparison (and determination of
lifetimes), dispersed fluorescence into the X, v = 1 level was
recorded (blue excitation spectrum). Displayed on the same scale,
virtually no dispersed fluorescence from the I state is visible. In
the TC-RFWM spectra transitions to the I state are also weaker but
clearly assignable. Overlaps of the probed B-X lines cause additional
features (*) to appear. This is most apparent for the P(13) probe
transition where overlap with the iP(9) line of 63Cu65Cu
adds additional features to the spectrum (iP(9), iQ(9), iR(9); the
label “i” is used to distinguish transitions of the
isotopologue). The red dotted lines are simulations based on the
fitted molecular constants. The presence of Q lines in the I-X
transition allows assignment to a 1Πu (1u)
term symbol for the I state, and their absence in the J-X transition
determines a 1Σ+ u (0+u)
symbol for the J state.
Identification of a new low energy 1u state in dicopper with resonant four-wave mixing
The low energy electronic structure of the copper dimer has been re-investigated using non-linear
four-wave mixing spectroscopy and high level ab initio calculations. In addition to the measurement
of the previously reported A, B, and C electronic states, a new state denoted A'
is identified with T0 = 20 100.4090(16) cm-1
(63Cu2). Rotational analysis of the A'-X (0,0) and (1,0) transitions leads to
the assignment of A' 1u. Ab initio calculations present the first theoretical description of the low energy
states of the copper dimer in Hund's case (c) and confirm the experimental assignment. The discovery
of this new low energy excited state emphasizes that spin-orbit coupling is significant in states with
d-hole electronic configurations and resolves a decades-long mystery in the initial assignment of the
In parallel, state-of-the-art high-level ab initio were performed considering the low energy states in Hund's case (c)
terms. The results prove the assertion that spin-orbit coupling is required to account
for the number of observable states.
Four-wave mixing spectra of Cu2. (a) depicts a DFWM spectrum of the (1,0) B1Σ+u
(0+u)- X 1Σ+g band. Inverted, a simulated spectrum for 63Cu2 and
63Cu65Cu is shown in green and red, respectively.
Simplified TC-RFWM spectra are obtained by intermediate labeling of specific rotational transitions (b)-(d).
Shedding light on a dark state: The energetically lowest high-spin state of C2
The Swan band emission between 400 and 700 nm is a prominent feature
in all carbon-containing flames. The intense d 3Πg-a 3Πu
electronic transition is widely used to detect the molecule in combustion
and astronomy studies to characterize and test chemical mechanisms.
The quantitative interpretation of spectra requires precise molecular
constants for the computation of the complex molecular spectra of C2.
In this work we report on the deperturbation of the
d 3Πg, v=6 state by double-resonant four-wave mixing. The high sensitivity and
dynamic range of the method allows observation of 'extra lines'. These
weak spectral features originate from nearby-lying, optically dark
states that gain transition strength through the perturbation process.
The study unveils the presence of the energetically lowest high-spin
state (5Πg) in the vicinity of the 3Πg, v=6
state and unravels major issues of the so-called high-pressure bands of C2. The anomalous nonthermal emission initially observed
in 1910 and later in numerous experimental environments are rationalized
by taking into account 'gateway' states, i.e. rotational levels
of the 3Πg, v=6 state that exhibit significant quintet character
through which all population flows from one electronic state to the
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Molecular anions are relevant in astronomy, in the upper atmosphere, in laboratory discharges and in combustion. Actually, anions are present in most combustion system and are assumed to play an important role in reactions forming pollutants like soot and aerosols from aircraft-engines. In a recent work, Warnatz and coworkers included negative ions in the chemical reaction mechanism of the modeling of a fuel-lean methane-oxygen flame and emphasized the relevance of anions. In particular, detailed reaction mechanisms involving negatively charged species are required for the calculations of the electrical conductivity which is essential for technical applications.|
Generally it is difficult to generate anions in sufficient abundance for spectroscopic studies. In fact, negative ions are far less abundant in most of the experimental environments than neutrals or cations. Often, anions are generated in a plasma where numerous species coexist whose spectra may overlap. Therefore, highly sensitive methods are required that are suitable for low-density environments. In addition, the identification and characterization of specific ions demands techniques exhibiting a substantial selectivity in order to disentangle the spectral features. An additonal challenge for spectroscopic investigations of anions is the binding energy of the excess electron that is usually small such that excited electronic states cannot exist.
In this work, we demonstrate for the first time to the best of our knowledge that nonlinear four-wave mixing is sufficiently sensitive for the detection of anions in a discharged free-jet. Both degenerate and four-wave mixing spectra of C2- are measured with an excellent signal to noise ratio. By comparison with cavity ring-down measurements under similar conditions, a detection limit for the carbon dimer anion of 107 anions/cm3 is estimated.
The result suggests convincingly that nonlinear four-wave mixing spectroscopy is applicable to study numerous neutral, cationic and anionic radicals that are produced in the controlled environment of a molecular beam by applying a discharged free-jet expansion.
The figure shows a DFWM spectrum of the C2 anion (upper trace). By applying two-color resonant four-wave mixing, the spectrum is simplified substantially. By tuning the PUMP laser to the (1,0) R1(6.5) transition and scanning the PROBE in the wavelength region of the sequence bands with Δν=0 four transitions are observed only: Two UP type transitions from the common J=6.5 level and two SEP transitions to J=7.5.
Deperturbation of the C2 Swan bands (d 3Πg - a 3Πu) by TC-RFWM
Numerous studies of the C2 radical reflect its importance in combustion, plasma and astro-chemistry. Recent LIF and polarization spectroscopy measurements have been performed to measure the absolute abundance in flames and plasma. However, a quantitative reduction of the measured data requires accurate molecular constants. These data are essential to compute the complex spectra exhibiting many overlapping transitions. In particular, an accurate simulation of the C2 spectra is essential in a combustion or plasma environment where spectral features from multiple components are present within the extended wavelength region of the Swan band.|
The determination of accurate molecular constants for the Swan bands is, however, difficult owing to the heavy line congestion and the numerous perturbations due to interactions with neighboring electronic states. In this work, we take advantage of the high sensitivity of four-wave mixing spectroscopy to investigate rotational perturbations occuring in the d 3Πg-a 3Πu electronic system of C2 in a discharged free-jet. We use intermediate level labeling by the double-resonance capabilites of the method to simplify the congested spectra for unambiguous assignments of perturbed and perturbing transitions. The investigations yield coupling constants that allow improved spectral simulations of C2 Swan band.
A DFWM of a heavily perturbed region of the C2 Swan band is shown (black trace). Two TC-RFWM scans by labeling the F2(8) and F1(14) rotational states, respectively, in the a 3Πu ground electronic state are shown in the upper trace. Unambigously, the perturbed R2(8) and R1(14) transitions are observed. In addition, transitions labeled by R2(8)* and R1(14)* are observed due to the "perturbing" levels of the B 1Δg. The lowest two traces (red and green) show the spectral simulation which accounts for the d 3Πg - B 1Δg interaction.
Rotationally resolved double-resonance spectroscopy of low-lying vibrational ground-state levels of HC4S
HCnS chains (n ≤ 2–8) have been subject to several
studies by different spectroscopic techniques due to the
relatively high abundance of sulfur in the interstellar
medium and the identification of sulfur containing
carbon chains by radio astronomy. To develop the application of the four-wave mixing technique to radicals produced in a slit-jet discharge, we performed an investigation on 2π3/2 symmetry rovibronic levels in the range of 549 and 580 cm-1 above the electronic ground state of HC4S. The levels are observed by applying two-color resonant four-wave mixing in a pulsed-discharge slit-jet expansion. Excitation is achieved via selected rotational transitions in the origin band 000 of the Ã 2π3/2 - X̃ 2π3/2 electronic transition. By combining the new measurements with recent spectroscopic data for the Ã 2π3/2 state, the origin band and the rotational constants for the 51 (CS stretching) and 8191 (bending) modes are determined.
TC-RFWM SEP spectrum of HC4S. Several R-transitions in the bandhead of the 000
Ã 2π3/2 - X̃ 2π3/2 transition are simulantaneously excited by tuning the PUMP laser to 19982.58 cm-1. By scanning the DUMP laser an overview of the ground state vibrational levels in the vicinity of 51 are observed.
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