Laser-produced plasma coupled with optical emission spectroscopy (OES) is a promising technique for detecting certain isotopes, with unique capabilities such as standoff and rapid detection and minimal to no sample preparation requirements. The key figure-of-merit for isotopic analysis using optical spectroscopy tools is the linewidth relative to the isotope shift. Although the isotopes of hydrogen (1H, 2H, and 3H) possess large isotopic shifts (1H–2H ≈ 180 pm, 1H–3H ≈ 240 pm), being a light element, the H transitions are susceptible to various broadening mechanisms in the plasma environment. One of the critical parameters that influence the linewidth of a transition in an LPP is the incident laser energy. In the present study, we evaluated the role of laser energy on plume expansion dynamics, deuterium emission intensity, and linewidth in a nanosecond laser-produced Zircaloy-4 plasma. The changes in 2Hα emission intensity and linewidth were investigated for varying laser fluence and time after plasma onset. Spatially resolved and spatially integrated OES were performed and compared to investigate the emission spectral features and linewidth of 2Hα. Monochromatic two-dimensional time-resolved imaging was also performed to understand the morphology of the deuterium and protium emission relative to all species in the plume. Our results showed that 1Hα and 2Hα emissions predominantly occur closer to the target. Measurements of 2Hα linewidth approached similar values at later times of plasma evolution regardless of the laser energy. The linewidths of the 2Hα transition showed insignificant differences between spatially resolved and spatially integrated measurements.