DOI: 10.1002/cphc.
201601131 Editorial
Physics and Chemistry with Cold Molecules
John M. Doyle,*[a] Bretislav Friedrich,*[b] and Edvardas Narevicius*[c]
T he previous century saw the emergence of techniques that
made it possible to extract microscopic informationand un-
derstandingfrom the chaos of macroscopic gaseous and
other systems. Among the first was the molecular beam tech-
nique that demonstrated the principal virtues of controlled
atomic and molecular motion for elucidating the burning
questions of the day, including those concerning the validity of
quantum mechanics. As emphasized by Otto Stern in 1946,[1]
the most distinctive characteristic property of the molecular
ray method is its simplicity and directness. It enables us to
make measurements on isolated neutral atoms or molecules
with macroscopic tools. For this reason it is especially valuable
for testing and demonstrating directly fundamental assump-
tions of the theory. In his 1988 article[2] Molecular Beams: our
legacy from Otto Stern, Norman Ramsey compiled a list of
what he called major contributions to physics from the field
of molecular beams. There were thirty two items on that list,
ranging from space quantization to molecular scattering to
tests of time reversal symmetry. In the 1960s, the molecular
beam technique made inroads into chemistry as well, by fulfill-
ing the pipe dream of disentangling from gaseous chaos ele-
mentary chemical reactions as single binary collisions of chemi-
cally well-defined reagents.[3] Chemical reaction dynamics that
came about as a result has remained one of the chief preoccu-
pations of chemical/molecular physics to date.
In the 1990s, yet another pipe dream came about that was
triggered by the renaissance then taking place in atomic phys-
ics.[4] This renaissance was nurtured by the development of
techniques to cool and slow down atoms. Based on a combina-
tion of molecular beams with laser cooling, these techniques
enabled to reach a regime where interatomic interactions were
governed by s-wave scattering, and ultimately led to the reali-
zation of quantum degeneracy in atomic gases. No sooner had
cold atoms become the talk of physicists worldwide than cold
molecules appeared as a pipe dream of molecular physicists
and physical chemists. For unlike atoms, molecules possess vi-
[a] Prof. J. M. Doyle
Harvard University, Department of Physics
17 Oxford Street, Cambridge, MA 02138 (USA)
E-mail: doyle@physics.harvard.edu
[b] Prof. B. Friedrich
Fritz-Haber-Institut der Max-Planck-Gesellschaft
Faradayweg 46, D-14195 Berlin (Germany)
E-mail: brich@fhi-berlin.mpg.de
[c] Prof. E. Narevicius
Chemical Physics Department
Perlman Chemical Sciences Building, Room 119A
Weizmann Institute of Science, 76100 Rehovot (Israel)
E-mail: edvardas.narevicius@weizmann.ac.il
ChemPhysChem 2016, 17, 1 2
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brational and rotational degrees of freedom and can be polar,
that is, carry a nonzero body-fixed electric dipole moment.
Ever since the late 1990s, this has been widely regarded in the
atomic, molecular and optical physics community as well by
physical chemists as a non-trivial enrichment of the repertoire
offered by cold atoms and therefore worthy of exploring.
T his Special Issue of ChemPhysChem, dedicated to cold mole-
cules, is a testimonial to where these explorations have led us
so far.
T he invited papersthere are twenty eight of themfall into
several, partly overlapping categories. The thickest batch of
contributions addresses the recalcitrant problem of producing
translationally cold molecules. Most of the techniques devel-
oped make use of molecular beamsincreasingly of the
buffer-gas beam varietyand of spatially and temporally
shaped static electric and magnetic as well as radio frequency,
microwave and optical fields. The techniques offer either
pulses or continuous streams of slow molecules whose veloci-
ties are in the 10 m s 1 range (buffer-gas beams alone yield
speeds of about 50100 m s 1). Also covered in the Special
Issue is the production of translationally ultracold molecules
from ultracold atoms via optical and Raman association and
population transfer techniques as well as direct laser cooling
of molecular beams.
Excitation dynamics, including to and with Rydberg states, as
revealed in collisional studies is another major theme of the
Special Issue. State-of-the-art experiments prove capable of
providing a high-definition image of inelastic scattering chan-
nels due to precise control of internal and translational de-
grees of freedom of the electrically neutral collision partners.
Ionmolecule scattering studies of reactive channels at colli-
sion energies down to the Kelvin range are showcased in an-
other batch of invited papers. Like the work mentioned above
on the neutrals, the ionmolecule studies make use of the
merged-beam technique that is capable of greatly reducing
the collision energy. The requisite cooling of the ions internal
degrees of freedom as well as of their translation is achieved
sympathetically, either by thermalizing the ions in question
with a cloud of ultracold atoms or with cryogenic helium
buffer gas. Apart from insights into the reaction dynamics, also
the elucidation of the properties of stabilized ion-molecule re-
action intermediates is reported. These ion papers are com-
plemented by a state-of-the-art vibrational spectroscopy study
of trapped ion clusters.
1  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim &

T he progress on the subject of controlling molecular rotation,
including the production of directional (aligned/oriented)
states, is described in a quintet of papers whose emphasis
ranges from super-rotors to Efimov states to the separation of
species and states via optical deflection. Some of the studies
identify a gyroscopic effect that ensures the preservation of
the alignment of rotational angular momentum throughout
a sequence of many collisions.
Two invited papers deal with molecules embedded in super-
fluid helium nanodroplets. A recent description of the embed-
ded molecules as quasi-particles made it possible to under-
stand quantitatively the renormalization of the molecular mo-
ments of inertia in the droplets and provided further insights
into this intriguing many-body problem. One of the papers
generalizes the quasiparticle approach to the case when the
embedded molecule is polar and the whole system subject to
an electrostatic field. The second paper appearing in this Spe-
cial Issue deals with systematic effects observed for the case of
molecular clusters self-assembled within a helium nanodroplet.
& ChemPhysChem 2016, 17, 1 2 www.chemphyschem.org
Editorial
Finally, a couple of papers analyze the behavior of polar mole-
cules cold enough to be trapped in an optical lattice and ex-
ploited for simulations of double-well behavior or for universal
quantum computing. Whether realizable in the near future or
not, systems of trapped molecules offer themselves as subjects
for archetypal studies that often lead to analytic results.
We hope that the readers of the Special Issue of ChemPhys-
Chem Physics and Chemistry with Cold Molecules will partake
in the enthusiasm for the field of the authors and guest editors
alike as well as share their view that much of the work done in
the gas phase to answer the burning questions of our day is
ever more relying on cold molecules.
[1] Otto Stern, Nobel Lectures, Physics 19421962, 1964, Amsterdam: Elsevier
Publishing Company.
[2] N. Ramsey, Z. Phys. D 1988, 10, 121.
[3] D. Herschbach, Adv. Chem. Phys. 1966, 10, 319 393.
[4] D. Kleppner, Rev. Mod. Phys. 1999, 71, S78 S84.
2  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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