Bridging quantum mechanics and nonlinear optics in Raman scattering

Abstract

We present a theoretical framework for spontaneous Raman scattering that fundamentally bridges quantum-mechanical and nonlinear-optical approaches. By conceptualizing spontaneous Raman scattering as a stimulated Raman gain or loss event seeded by the quantum vacuum field, we rigorously derive the spontaneous Raman cross-section directly from the third-order nonlinear susceptibility. Crucially, this framework predicts the existence of a hitherto unrecognized phenomenon: "spontaneous Raman loss" (sRL), which acts as the vacuum-seeded counterpart to stimulated Raman loss, complementing traditional spontaneous Raman scattering (spontaneous Raman gain, sRG). Furthermore, we establish a rigorous connection to the traditional Kramers-Heisenberg-Dirac (KHD) theory, revealing that the spontaneous process is governed by interference before a detector between the signal field emitted from molecules and the vacuum field itself that stimulates the molecules. This insight uncovers a direct correspondence between the sRG susceptibility and the rotating/counter-rotating interference terms in the KHD formula. Ultimately, we extend the foundational KHD theory by incorporating previously unrecognized essential terms, achieving perfect analytical agreement between the quantum mechanical and nonlinear optical descriptions of Raman scattering.