Heart rate variability (HRV) is an important indicator of autonomic nervous system activity and can be used for the identification of affective states. The development of remote Photoplethysmography (rPPG) technology has made it possible to measure pulse rate variability (PRV) using a camera without any sensor-skin contact, which is highly correlated to HRV, thus, enabling contactless assessment of emotional states. In this study, we employed ten machine learning techniques to identify emotions using camera-based PRV features. Our experimental results show that the best classification model achieved a coordination correlation coefficient of 0.34 for value recognition and 0.36 for arousal recognition. The rPPG-based measurement has demonstrated promising results in detecting HAHV (high-arousal high-valence) emotions with high accuracy. Furthermore, for emotions with less noticeable variations, such as sadness, the rPPG-based measure outperformed the baseline deep network for facial expression analysis.