Recent experiments showed that the chemical reaction rate is modified, either increased or decreased, by strongly coupling a nuclear vibration mode to the single mode of an optical cavity. Herein we investigate how the rate of an electron-transfer reaction depends on the molecule-cavity coupling in the ultrastrong coupling regime, where the coupling strength is comparable in magnitude with both the vibrational and the cavity frequencies. We found two main factors that determine the modification of the reaction rate: the relative shifts of the energy levels induced by the coupling and the mixing of the ground and excited states of molecular vibration in the ground state of the hybrid molecule-plus-cavity system through which the Franck-Condon factor between the initial and final states of the transition is altered. The former is the dominant factor if the molecule-cavity coupling strengths for the reactant and product states differ significantly from each other and gives rise to an increase in the reaction rate over a wide range of system’s parameters. The latter dominates if the coupling strengths and energy levels of the reactant and product states are close to each other and it leads to a decrease in the reaction rate. The effect of the mixing of molecular vibrational states on the reaction rate is, however, suppressed in a system containing a large number of molecules due to the collective nature of the resulting polariton, and thus should be observed in a system containing a small number of molecules. In contrast, the effect of the relative shifts of the energy levels should be essentially independent of the number of molecules coupled to the cavity.

We formulate a self-consistent Hartree-Fock theory for a spin-1 Bose gas at finite temperature and apply it to characterizing the phase diagram. We find that spin coherence between thermal atoms in different magnetic sub-levels develops via coherent collisions with the condensed atoms, and is a crucial factor in determining the phase diagram. We develop analytical expressions to characterize the interaction and temperature dependent shifts of the phase boundaries.

We investigate the effects of thermal and quantum fluctuations on the phase diagram of a spin-1 87 Rb Bose-Einstein condensate (BEC) under the quadratic Zeeman effect. Due to the large ratio of spin-independent to spin-dependent interactions of 87 Rb atoms, the effect of noncondensed atoms on the condensate is much more significant than that in scalar BECs. We find that the condensate and spontaneous magnetization emerge at different temperatures when the ground state is in the broken-axisymmetry phase. In this phase, a magnetized condensate induces spin coherence of noncondensed atoms in different magnetic sublevels, resulting in temperature-dependent magnetization of the noncondensate. We also examine the effect of quantum fluctuations on the order parameter at absolute zero and find that the ground-state phase diagram is significantly altered by quantum depletion.

Spinor Bose-Einstein condensates provide a unique example in which the Bogoliubov theory fails to describe the metastability associated with first-order quantum phase transitions. This problem is resolved by developing the spinor Beliaev theory which takes account of quantum fluctuations of the condensate. It is these fluctuations that generate terms of higher than the fourth order in the order-parameter field which are needed for the first-order phase transitions. Besides the conventional first-order phase transitions which are accompanied by metastable states, we find a class of first-order phase transitions which are not accompanied by metastable states. The absence of metastability in these phase transitions holds to all orders of approximation since the metastability is prohibited by the symmetry of the Hamiltonian at the phase boundary. Finally, the possibility of macroscopic quantum tunneling from a metastable state to the ground state is discussed.