the data point at U = 10 kV in the evaluation of the mean
value of w.
Interestingly, for both isomers the susceptibility values differ
from the computed static polarizabilities. This is consistent
with the presence of vibration-activated electric dipole moments
which emerge for flexible molecules at high temperature.6
Based on our earlier experiments with perfluoroalkyl-
functionalized azobenzenes19 we expect a thermal contribution
to the susceptibility of 10–15 A3 ꢁ 4pe0 per side chain.
Summarizing, the different total susceptibilities of both
constitutional isomers lead to different de Broglie interference
shifts in the presence of external fields. The isomers thus are
distinguishable even by pure center-of-mass interferometry, in
spite of their identical mass and chemical sum formula.
Our work was supported by the Austrian FWF within the
programs Wittgenstein Z149-N16, DK-W1210 CoQuS, the
Swiss National Science Foundation and ESF EuroQuasar
MIME.
Fig. 2 Experimental values of wstat for compounds 1 (blue full circles)
and 2 (red hollow circles) extracted from the interference fringe shift at
different settings of the deflection voltage. The error bars represent the
statistical errors (1s). The solid blue and red lines show the weighted
means of the susceptibility values of 1 and 2, respectively (see
Supporting Information).
contributions will be comparable for both constitutional
isomers 1 and 2.
Notes and references
Compounds 1 and 2 were examined in two separate experi-
mental runs. They were evaporated at identical temperatures,
but we chose slightly different velocity distributions. These
were centered at nmean = 110 m sꢀ1 for compound 1 and
nmean = 91 m sꢀ1 for 2 with DnFWHM/nmean = 0.15 and
DnFWHM/nmean = 0.10, respectively. This corresponds to a
mean de Broglie wavelength of about 2.5 pm.
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Each individual interference pattern was sampled in steps of
Dx3 = 26 nm over a range of 1064 nm, corresponding to four
full interference fringe periods. The interference patterns were
recorded at different voltage settings.
At high voltages the fringe visibility is reduced by a velocity
dependent dephasing of the interference pattern and the finite
width of the velocity distribution. Since Dx3 is velocity dependent
(eqn (I)), a large velocity spread will blur the interference
contrast.
8 S. Wu, M. T. Gonzalez, R. Huber, S. Grunder, M. Mayor,
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¨
9 R. Huber, M. T. Gonza
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lez, S. Wu, M. Langer, S. Grunder,
V. Horhoiu, M. Mayor, M. R. Bryce, C. Wang, R. Jitchati,
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¨
In order to minimize the effect of thermal drifts of the
grating position, the field-dependent fringe shift was read for
each deflection voltage separately. For each position of G3 the
molecular beam transmission was measured both at the
desired deflection voltage and for a reference value of U = 1 kV.
The electric susceptibility was determined for every single
voltage step by fitting eqn (I) to the experimental value of Dx3
with wstat as the only free parameter. The calculation included
the detailed measured velocity distribution. The results of all
runs for both molecules are depicted in Fig. 2. We find a
weighted mean of wstat = 102 ꢃ 0.8 A3 ꢁ 4pe0 for compound 1
and wstat = 126 ꢃ 0.5 A3 ꢁ 4pe0 for 2. We show only the
statistical error bar, which decreases because of the more
reliable reading at high fringe deflection and high voltages.
The systematic error is dominated by the uncertainty in the
velocity measurement as well as the knowledge of both laser
power and focal width. The drop in interference contrast spoils
the fit quality at high deflection voltage. We therefore exclude
12 E. Lortscher, M. Elbing, M. Tschudy, C. v. Hanisch, H. B. Weber,
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M. Mayor and H. Riel, ChemPhysChem, 2008, 9, 2252.
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15 EA of 8 is missing due to limited stability.
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H. Ulbricht, M. Gring, F. Goldfarb, T. Savas, M. Muri,
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M. Mayor and M. Arndt, Nat. Phys., 2007, 3, 711.
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¨
ꢂc
This journal is The Royal Society of Chemistry 2010
Chem. Commun., 2010, 46, 4145–4147 | 4147